Vertical profiling of SO2 and SO above Venus’ clouds by SPICAV/SOIR solar occultations

New measurements of sulfur dioxide (SO₂) and monoxide (SO) in the atmosphere of Venus by SPICAV/SOIR instrument onboard Venus Express orbiter provide ample statistics to study the behavior of these gases above Venus’ clouds. The instrument (a set of three spectrometers) is capable to sound atmospheric structure above the clouds in several observation modes (nadir, solar and stellar occultations) either in the UV or in the near IR spectral ranges. We present the results from solar occultations in the absorption ranges of SO₂ (190–230 nm, and at 4 μm) and SO (190–230 nm). The dioxide was detected by the SOIR spectrometer at the altitudes of 65–80 km in the IR and by the SPICAV spectrometer at 85–105 km in the UV. The monoxide’s absorption was measured only by SPICAV at 85–105 km. We analyzed 39 sessions of solar occultation, where boresights of both spectrometers are oriented identically, to provide complete vertical profiling of SO₂ of the Venus’ mesosphere (65–105 km). Here we report the first firm detection and measurements of two SO₂ layers. In the lower layer SO₂ mixing ratio is within 0.02–0.5 ppmv. The upper layer, also conceivable from microwave measurements by Sandor et al. (Sandor, B.J., Todd Clancy, R., Moriarty-Schieven, G., Mills, F.P. [2010]. Icarus 208, 49–60) is characterized by SO₂ increasing with the altitude from 0.05 to 2 ppmv, and the [SO₂]/[SO] ratio varying from 1 to 5. The presence of the high-altitude SO_x species could be explained by H₂SO₄ photodissociation under somewhat warmer temperature conditions in Venus mesosphere. At 90–100 km the content of the sulfur dioxide correlates with temperature increasing from 0.1 ppmv at 165–170 K to 0.5–1 ppmv at 190–192 K. It supports the hypothesis of SO₂ production by the evaporation of H₂SO₄ from droplets and its subsequent photolysis at around 100 km.     

Thermal structure and CO distribution for the Venus mesosphere/lower thermosphere: 2001–2009 inferior conjunction sub-millimeter CO absorption line observations

Sub-millimeter ¹²CO (346 GHz) and ¹³CO (330 GHz) line absorptions, formed in the mesosphere and lower thermosphere of Venus (70–120 km), have been mapped across the nightside Venus disk during 2001–2009 inferior conjunctions, employing the James Clerk Maxwell Telescope (JCMT). Radiative transfer analysis of these thermal line absorptions supports temperature and CO mixing profile retrievals, as well as Doppler wind fields (described in the companion paper, Clancy et al., 2012). Temporal sampling over the hourly, daily, weekly and interannual timescales was obtained over 2001–2009. On timescales inferred as several weeks, we observe changes between very distinctive CO and temperature nightside distributions. Retrieved nightside CO, temperature distributions for January 2006 and August 2007 observations display strong local time, latitudinal gradients consistent with early morning (2–3 am), low-to-mid latitude (0–40NS) peaks of 100–200% in CO and 20–30 K in temperature. The temperature increases are most pronounced above 100 km altitudes, whereas CO variations extend from 105 km (top altitude of retrieval) down to below 80 km in the mesosphere. In contrast, the 2004 and 2009 periods of observation display modest temperature (5–10 K) and CO (30–60%) increases, that are centered on antisolar (midnight) local times and equatorial latitudes. Doppler wind derived global (zonal and should be SSAS) circulations from the same data do not exhibit variations correlated with these CO, temperature short-term variations. However, large-scale residual wind fields not fit by the zonal, SSAS circulations are observed in concert with the strong temperature, CO gradients observed in 2006 and 2007 (Clancy et al., 2010). These short term variations in nightside CO, temperature distributions may also be related to observed nightside variations in O₂ airglow (Hueso, H., Sánchez-Lavega, A., Piccioni, G., Drossart, P., Gérard, J.C., Khatuntsev, I., Zasova, L., Migliorini, A. [2008]. J. Geophys. Res. 113, E00B02. doi:10.1029/2008JE003081) and upper mesospheric SO and SO₂ layers (Sandor, B.J., Clancy, R.T., Moriarty-Schieven, G.H., Mills, F.P. [2010]. Icarus 208, 49–60).The retrieved temperature profiles also exhibit 20 K long-term (2001–2009) variations in nightside (whole disk) average mesospheric (80–95 km) temperatures, similar to 1982–1991 variations identified in previous millimeter CO line observations (Clancy et al., 1991). Global average diurnal variations in lower thermospheric temperatures and mesospheric CO abundances decreased by a factor-of-two between 2000–2002 versus 2007–2009 periods of combined dayside and nightside observations. The infrequency and still limited temporal extent of the observations make it difficult to assign specific timescales to such longer term variations, which may be associated with longer term variations observed for cloud top SO₂ (Esposito, L.W., Bertaux, J.-L., Krasnopolsky, V., Moroz, V.I., Zasova, L.V. [1997]. Chemistry of lower atmosphere and clouds. In: Bougher, S.W., Hunten, D.M., Phillips, R.J. (Eds.), VENUS II, 1362pp) and mesospheric water vapor (Sandor, B.J., Clancy, R.T. [2005]. Icarus 177, 129–143) abundances.     

Sulfur chemistry in the middle atmosphere of Venus

Venus Express measurements of the vertical profiles of SO and SO₂ in the middle atmosphere of Venus provide an opportunity to revisit the sulfur chemistry above the middle cloud tops (～58 km). A one dimensional photochemistry-diffusion model is used to simulate the behavior of the whole chemical system including oxygen-, hydrogen-, chlorine-, sulfur-, and nitrogen-bearing species. A sulfur source is required to explain the SO₂ inversion layer above 80 km. The evaporation of the aerosols composed of sulfuric acid (model A) or polysulfur (model B) above 90 km could provide the sulfur source. Measurements of SO₃ and SO (a¹Δ → X³Σ^-) emission at 1.7 μm may be the key to distinguish between the two models.     

A photochemical model for the Venus atmosphere at 47–112 km

The model is intended to respond to the recent findings in the Venus atmosphere from the Venus Express and ground-based submillimeter and infrared observations. It extends down to 47 km for comparison with the kinetic model for the lower atmosphere (Krasnopolsky, V.A. [2007]. Icarus 191, 25–37) and to use its results as the boundary conditions. The model numerical accuracy is significantly improved by reduction of the altitude step from 2 km in the previous models to 0.5 km. Effects of the NUV absorber are approximated using the detailed photometric observations at 365 nm from Venera 14. The H₂O profile is not fixed but calculated in the model. The model involves odd nitrogen and OCS chemistries based on the detected NO and OCS abundances. The number of the reactions is significantly reduced by removing of unimportant processes. Column rates for all reactions are given, and balances of production and loss may be analyzed in detail for each species.The calculated vertical profiles of CO, H₂O, HCl, SO₂, SO, OCS and of the O₂ dayglow at 1.27 μm generally agree with the existing observational data; some differences are briefly discussed. The OH dayglow is ～30 kR, brighter than the OH nightglow by a factor of 4. The H + O₃ process dominates in the nightglow excitation and O + HO₂ in the dayglow, because of the reduction of ozone by photolysis. A key feature of Venus’ photochemistry is the formation of sulfuric acid in a narrow layer near the cloud tops that greatly reduces abundances of SO₂ and H₂O above the clouds. Delivery of SO₂ and H₂O through this bottleneck determines the chemistry and its variations above the clouds. Small variations of eddy diffusion near 60 km result in variations of SO₂, SO, and OCS at and above 70 km within a factor of ～30. Variations of the SO₂/H₂O ratio at the lower boundary have similar but weaker effect: the variations within a factor of ～4 are induced by changes of SO₂/H₂O by ±5%. Therefore the observed variations of the mesospheric composition originate from minor variations of the atmospheric dynamics near the cloud layer and do not require volcanism. NO cycles are responsible for production of a quarter of O₂, SO₂, and Cl₂ in the atmosphere. A net effect of photochemistry in the middle atmosphere is the consumption of CO₂, SO₂, and HCl from and return of CO, H₂SO₄, and SO₂Cl₂ to the lower atmosphere. These processes may be balanced by thermochemistry in the lower atmosphere even without outgassing from the interior, though the latter is not ruled out by our models. Some differences between the model and observations and the previous models are briefly discussed.     

Search for methane and upper limits to ethane and SO2 on Mars

The IRTF/CSHELL observations in February 2006 at L_S = 10° and 63–93°W show ～10 ppb of methane at 45°S to 7°N and ～3 ppb outside this region that covers the deepest canyon Valles Marineris. Observations in December 2009 at L_S = 20° and 0–30°W included spectra of the Moon at a similar airmass as a telluric calibrator. A technique for extraction of the martian methane line from a combination of the Mars and Moon spectra has been developed. The observations reveal no methane with an upper limit of 8 ppb. The results of both sessions agree with the observations by Mumma et al. (Mumma, M.J. et al. [2009]. Science 323, 1041–1045) at the same season in February 2006 and are smaller than those in the PFS and TES maps. Production and removal of the biological methane on Mars do not significantly change the redox state of the atmosphere and the balance of hydrogen. A search for ethane at 2977 cm^?1 results in an upper limit of 0.2 ppb. However, this limit does not help to establish the origin of methane on Mars. Reanalysis of our search for SO₂ using TEXES confirms the recently established upper limit of 0.3 ppb. Along with the lack of hot spots and gas vents with endogenic heat sources in the THEMIS observations, the very low upper limit to SO₂ on Mars does not favor geological methane that is less abundant than SO₂ in the outgassing from the terrestrial planets.     

Characterizing Io’s Pele,Tvashtar and Pillan plumes: Lessons learned from Hubble

Hubble Space Telescope/Wide Field and Planetary Camera 2 (HST/WFPC2) images of Io obtained between 1995 and 2007 between 0.24 and 0.42 μm led to the detection of the Pele plume in reflected sunlight in 1995 and 1999; imaging of the Pele plume via absorption of jovian light in 1996 and 1999; detection of the Prometheus-type Pillan plume in reflected sunlight in 1997; and detection of the 2007 Pele-type Tvashtar plume eruption in reflected sunlight and via absorption of jovian light. Based on a detailed analysis of these observations we characterize and compare the gas and dust properties of each of the detected plumes. In each case, the brightness of the plumes in reflected sunlight is less at 0.26 μm than at 0.33 μm. Mie scattering analysis of the wavelength dependence of each plume’s reflectance signature suggests that range of particle sizes within the plumes is quite narrow. Assuming a normal distribution of particle sizes, the range of mean particle sizes is ～0.035–0.12 μm for the 1997 Pillan eruption, ～0.05–0.08 μm for the 1999 Pele and 2007 Tvasthar plumes, and ～0.05–0.11 μm for the 1995 Pele plume, and in each case the standard deviation in the particle size distribution is <15%. The Mie analysis also suggests that the 2007 Tvashtar eruption released ～10⁹ g of sulfur dust, the 1999 Pele eruption released ～10⁹ g of SO₂ dust, the 1997 Pillan eruption released ～10¹⁰ g of SO₂ dust, and the 1995 Pele plume may have released ～10¹⁰ g of SO₂ dust. Analysis of the plume absorption signatures recorded in the F255W filter bandpass (0.24–0.28 μm) indicates that the opacity of the 2007 Tvashtar plume was 2× that of the 1996 and 1999 Pele plume eruptions. While the sulfur dust density estimated for the Tvashtar from the reflected sunlight data could have produced 61% of the observed plume opacity, <10% of the 1999 Pele F255W plume opacity could have resulted from the SO₂ dust detected in the eruption. Accounting for the remaining F255W opacity level of the Pele and Tvasthar plumes based on SO₂ and S₂ gas absorption, the SO₂ and S₂ gas density inferred for each plume is almost equivalent corresponding to ～2–6 × 10¹⁶ cm^?2 and 3–5 × 10¹⁵ cm^?2, respectively, producing SO₂ and S₂ gas resurfacing rates ～0.04–0.2 cm yr^?1 and 0.007–0.01 cm yr^?1; and SO₂ and S₂ gas masses ～1–4 × 10¹⁰ g and ～2–3 × 10⁹ g; for a total dust to gas ratio in the plumes ～10^?1–10^?2. The 2007 Tvashtar plume was detected by HST at ～380 ± 40 km in both reflected sunlight and absorbed jovian light; in 1999, the detected Pele plume altitude was 500 km in absorbed jovian light, but in reflected sunlight the detected height was ～2× lower. Thus, for the 1999 Pele plume, similar to the 1979 Voyager Pele plume observations, the most efficient dust reflections occurred in the region closest to the plume vent. The 0.33–0.42 μm brightness of the 1997 Pillan plume was 10–20× greater than the Pele or Tvashtar plumes, exceeding by a factor of 3 the average brightness levels observed within 200 km of 1979 Loki eruption vent. But, the 0.26 μm brightness of the 1997 Pillan plume in reflected sunlight was significantly lower than would be predicted by the dust scattering model. Presuming that the 0.26 μm brightness of the 1997 Pillan plume was attenuated by the eruption plume’s gas component, then an SO₂ gas density ～3–6 × 10¹⁸ cm^?2 is inferred from the data (for S₂/SO₂ ratios ?4%), comparable to the 0.3–2 × 10¹⁸ cm^?2 SO₂ density detected at Loki in 1979 (Pearl, J.C. et al. [1979]. Nature 280, 755; Lellouch et al., 1992), and producing an SO₂ gas mass ～3–8 × 10¹¹ g and an SO₂ resurfacing rate ～8–23 cm yr^?1. These results confirm the connection between high (?10¹⁷ cm^?2) SO₂ gas content and plumes that scatter strongly at nearly blue wavelengths, and it validates the occurrence of high density SO₂ gas eruptions on Io. Noting that the SO₂ gas content inferred from a spectrum of the 2003 Pillan plume was significantly lower ～2 × 10¹⁶ cm^?2 (Jessup, K.L., Spencer, J., Yelle, R. [2007]. Icarus 192, 24–40); and that the Pillan caldera was flooded with fresh SO₂ frost/slush just prior to the 1997 Pillan plume eruption (Geissler, P., McEwen, A., Phillips, C., Keszthelyi, L., Spencer, J. [2004a]. Icarus 169, 29–64; Phillips, C.B. [2000]. Voyager and Galileo SSI Views of Volcanic Resurfacing on Io and the Search for Geologic Activity at Europa. Ph.D. Thesis, Univ. of Ariz., Tucson); we propose that the density of SO₂ gas released by this volcano is directly linked to the local SO₂ frost abundance at the time of eruption.     

Observation of DCl and upper limit to NH3 on Venus

To search for DCl in the Venus atmosphere, a spectrum near the D³⁵Cl (1–0) R4 line at 2141.54 cm^?1 was observed using the CSHELL spectrograph at NASA IRTF. Least square fitting to the spectrum by a synthetic spectrum results in a DCl mixing ratio of 17.8 ± 6.8 ppb. Comparing to the HCl abundance of 400 ± 30 ppb (Krasnopolsky [2010a] Icarus, 208, 314–322), the DCl/HCl ratio is equal to 280 ± 110 times the terrestrial D/H = 1.56 × 10^?4. This ratio is similar to that of HDO/H₂O = 240 ± 25 times the terrestrial HDO/H₂O from the VEX/SOIR occultations at 70–110 km. Photochemistry in the Venus mesosphere converts H from HCl to that in H₂O with a rate of 1.9 × 10⁹ cm^?2 s^?1 (Krasnopolsky [2012] Icarus, 218, 230–246). The conversion involves photolysis of HCl; therefore, the photochemistry tends to enrich D/H in HCl and deplete in H₂O. Formation of the sulfuric acid clouds may affect HDO/H₂O as well. The enriched HCl moves down by mixing to the lower atmosphere where thermodynamic equilibriums for H₂ and HCl near the surface correspond to D/H = 0.71 and 0.74 times that in H₂O, respectively. Time to establish these equilibriums is estimated at ～3 years and comparable to the mixing time in the lower atmosphere. Therefore, the enriched HCl from the mesosphere gives D back to H₂O near the surface. Comparison of chemical and mixing times favors a constant HDO/H₂O up to ～100 km and DCl/HCl equal to D/H in H₂O times 0.74.Ammonia is an abundant form of nitrogen in the reducing environments. Thermodynamic equilibriums with N₂ and NO near the surface of Venus give its mixing ratio of 10^?14 and 6 × 10^?7, respectively. A spectrum of Venus near the NH₃ line at 4481.11 cm^?1 was observed at NASA IRTF and resulted in a two-sigma upper limit of 6 ppb for NH₃ above the Venus clouds. This is an improvement of the previous upper limit by a factor of 5. If ammonia exists at the ppb level or less in the lower atmosphere, it quickly dissociates in the mesosphere and weakly affects its photochemistry.     

Mineral reaction buffering of Venus’ atmosphere: A thermochemical constraint and implications for Venus-like planets

The equilibrium suggested as a buffer for CO₂ in the Venus atmosphere, CaCO₃ + SiO₂ = CaSiO₃ + CO₂, cannot act as a buffer at the Venus surface/troposphere – the pressure–temperature slope of the equilibrium and that of the atmosphere (dry adiabat with significant greenhouse heating) do not provide buffering capacity (if indeed CaCO₃ were present). Instead, perturbations to T or P(CO₂) can produce catastrophic expansion or collapse of the atmosphere. This instability can be generalized to all devolatilization reactions that produce a radiatively active gas in a planetary atmosphere dominated by such gases, and gives a simple thermochemical criterion for whether a reaction could buffer such an atmosphere. Simple decarbonation reactions fail this criterion, suggesting that the abundance of CO₂ in a CO₂-dominated atmosphere cannot be buffered by chemical reactions with the surface; a similar conclusion holds for the abundance of H₂O in an H₂O-dominated (steam) atmosphere. Buffering of minor gases is more likely; a mineral buffer equilibrium for SO₂ proposed for Venus, FeS₂ + CO₂ = Fe₃O₄ + SO₂ + CO, passes the thermochemical criterion, as does a reaction involving Ca sulfate. These inferences can be generalized to atmospheres in ‘moist’ adiabatic equilibria, and to extrasolar Venus-like planets, and will help in interpreting the compositions of their atmospheres.     

The O2 nightglow in the martian atmosphere by SPICAM onboard of Mars-Express

We present observations of the O₂(a¹Δ_g) nightglow at 1.27 μm on Mars using the SPICAM IR spectrometer onboard of the Mars Express orbiter. In contrast to the O₂(a¹Δ_g) dayglow that results from the ozone photodissociation, the O₂(a¹Δ_g) nightglow is a product of the recombination of O atoms formed by CO₂ photolysis on the dayside at altitudes higher than 80 km and transported downward above the winter pole by the Hadley circulation. The first detections of the O₂(a¹Δ_g) nightglow in 2010 indicate that it is about two order of magnitude less intense than the dayglow (Bertaux, J.-L., Gondet, B., Bibring, J.-P., Montmessin, F., Lefèvre, F. [2010]. Bull. Am. Astron. Soc. 42, 1040; Clancy et al. [2010]. Bull. Am. Astron. Soc. 42, 1041). SPICAM IR sounds the martian atmosphere in the near-IR range (1–1.7 μm) with the spectral resolution of 3.5 cm^?1 in nadir, limb and solar occultation modes. In 2010 the vertical profiles of the O₂(a¹Δ_g) nightside emission have been obtained near the South Pole at latitudes of 82–83°S for two sequences of observations: L_s = 111–120° and L_s = 152–165°. The altitude of the emission maximum varied from 45 km on L_s = 111–120° to 38–49 km on L_s = 152–165°. Averaged vertically integrated intensity of the emission at these latitudes has shown an increase from 0.22 to 0.35 MR. Those values of total vertical emission rate are consistent with the OMEGA observations on Mars-Express in 2010. The estimated density of oxygen atoms at altitudes from 50 to 65 km varies from 1.5 × 10¹¹ to 2.5 × 10¹¹ cm^?3. Comparison with the LMD general circulation model with photochemistry (Lefèvre, F., Lebonnois, S., Montmessin, F., Forget, F. [2004]. J. Geophys. Res. 109, E07004; Lefèvre et al. [2008]. Nature 454, 971–975) shows that the model reproduces fairly well the O₂(a¹Δ_g) emission layer observed by SPICAM when the large field of view (>20 km on the limb) of the instrument is taken into account.     

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

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

Absolute magnitudes of asteroids and a revision of asteroid albedo estimates from WISE thermal observations

We obtained estimates of the Johnson V absolute magnitudes (H) and slope parameters (G) for 583 main-belt and near-Earth asteroids observed at Ond?ejov and Table Mountain Observatory from 1978 to 2011. Uncertainties of the absolute magnitudes in our sample are <0.21 mag, with a median value of 0.10 mag. We compared the H data with absolute magnitude values given in the MPCORB, Pisa AstDyS and JPL Horizons orbit catalogs. We found that while the catalog absolute magnitudes for large asteroids are relatively good on average, showing only little biases smaller than 0.1 mag, there is a systematic offset of the catalog values for smaller asteroids that becomes prominent in a range of H greater than ～10 and is particularly big above H ～ 12. The mean (H_catalog ? H) value is negative, i.e., the catalog H values are systematically too bright. This systematic negative offset of the catalog values reaches a maximum around H = 14 where the mean (H_catalog ? H) is ?0.4 to ?0.5. We found also smaller correlations of the offset of the catalog H values with taxonomic types and with lightcurve amplitude, up to ～0.1 mag or less. We discuss a few possible observational causes for the observed correlations, but the reason for the large bias of the catalog absolute magnitudes peaking around H = 14 is unknown; we suspect that the problem lies in the magnitude estimates reported by asteroid surveys. With our photometric H and G data, we revised the preliminary WISE albedo estimates made by Masiero et al. (Masired, J.R. et al. [2011]. Astrophys. J. 741, 68–89) and Mainzer et al. (Mainzer, A. et al. [2011b]. Astrophys. J. 743, 156–172) for asteroids in our sample. We found that the mean geometric albedo of Tholen/Bus/DeMeo C/G/B/F/P/D types with sizes of 25–300 km is p_V = 0.057 with the standard deviation (dispersion) of the sample of 0.013 and the mean albedo of S/A/L types with sizes 0.6–200 km is 0.197 with the standard deviation of the sample of 0.051. The standard errors of the mean albedos are 0.002 and 0.006, respectively; systematic observational or modeling errors can predominate over the quoted formal errors. There is apparent only a small, marginally significant difference of 0.031 ± 0.011 between the mean albedos of sub-samples of large and small (divided at diameter 25 km) S/A/L asteroids, with the smaller ones having a higher albedo. The difference will have to be confirmed and explained; we speculate that it may be either a real size dependence of surface properties of S type asteroids or a small size-dependent bias in the data (e.g., a bias towards higher albedos in the optically-selected sample of asteroids). A trend of the mean of the preliminary WISE albedo estimates increasing with asteroid size decreasing from D ～ 30 down to ～5 km (for S types) showed in Mainzer et al. (Mainzer, A. et al. [2011a]. Astrophys. J. 741, 90–114) appears to be mainly due to the systematic bias in the MPCORB absolute magnitudes that progressively increases with H in the corresponding range H = 10–14.     

The growth of wind-waves in Titan’s hydrocarbon seas

Ocean wave growth on Titan is considered. The classic Sverdrup–Munk theory for terrestrial wave growth is applied to Titan, and is compared with a simple energy balance model that exposes the effect of Titan’s environmental parameters (air density, gravity, and fluid density). These approaches are compared with the only previously-published (semi-empirical) model (Ghafoor, N.A.-L., Zarnecki, J.C., Challenor, P., Srokosz, M.A. [2000] J. Geophys. Res. 105, 12,077–12,091, hereafter G2k), and allow the impact of various parameters such as atmospheric density to be transparently explored.Our model, like G2k, suggests fully-developed significant wave heights on Titan H_s = 0.2 U², where U is the windspeed (SI units): in dimensionless terms this is rather close to H_s = 0.2 U²/g, a rule of thumb previously noted for terrestrial waves (we find various datasets where the prefactor varies by ～2). It is noted that liquid and air densities affect the growth rate of waves, but not their fully-developed height: for 1 m/s winds wave amplitude reaches 0.15 m (75% of fully-developed) with a fetch of only 1 km, rather faster than predicted by G2k. Liquid viscosity has no major effect on gravity wave growth, but does influence the threshold windspeed at which gravity–capillary waves form in the first place.The model is used to develop predicted ranges for wave height to guide the design of the Titan Mare Explorer (TiME), a proposed Discovery-class mission to float a capsule on Ligeia Mare in 2023. For the expected maximum 1 m/s winds, a significant wave height of 0.2 m and wavelength of ～4 m can be expected. Assuming that wave heights follow Rayleigh statistics as they do on Earth, then given the wave period of ～4 s, individual waves of ～0.6 m might be encountered over a 3 month period.For predicted Titan winds at Kraken Mare, significant wave heights may reach ～0.6 m in the peak of summer but do not exceed the tidal amplitude at its northern end, consistent with the area around Mayda Insula being a tidal flat, while elsewhere on Kraken and Ligeia and at Ontario Lacus, shorelines may be wave- or tidally-dominated, depending on the specific location.     

Spatial variability,composition and thickness of the seasonal north polar cap of Mars in mid-spring

The planetary fourier spectrometer (PFS) for the Mars express mission (MEX) is an infrared spectrometer operating in the wavelength range from 1.2 to 45 μm by means of two spectral channels, called SWC (short wavelength channel) and LWC (long wavelength channel), covering, respectively, 1.2–5.5 and 5.5–45 μm.The middle-spring Martian north polar cap (Ls∼40°) has been observed by PFS/MEX in illuminated conditions during orbit 452. The SWC spectra are here used to study the cap composition in terms of CO₂ ice, H₂O ice and dust content. Significant spectral variation is noted in the cap interior, and regions of varying CO₂ ice grain sizes, water frost abundance, CO₂ ice cover and dust contamination can be distinguished. In addition, we correlate the infrared spectra with an image acquired during the same orbit by the OMEGA imaging spectrometer and with the altimetry from MOLA data. Many of the spectra variations correlate with heterogeneities noted in the image, although significant spectral variations are not discernible in the visible. The data have been divided into five regions with different latitude ranges and strong similarities in the spectra, and then averaged. Bi-directional reflectance models have been run with the appropriate lighting geometry and used to fit the observed data, allowing for CO₂ ice and H₂O ice grain sizes, dust and H₂O ice contaminations in the form of intimate granular mixtures and spatial mixtures.A wide annulus of dusty water ice surrounds the recessing CO₂ seasonal cap. The inner cap exhibits a layered structure with a thin CO₂ layer with varying concentrations of dark dust, on top of an H₂O ice underneath ground. In the best-fits, the ices beneath the top layer have been considered as spatial mixtures. The results are still very good everywhere in the spectral range, except where the CO₂ ice absorption coefficients are such that even a thin layer is enough to totally absorb the incoming radiation (i.e. the band is saturated). This only happens around 3800 cm⁻¹, inside the strong 2.7-μm CO₂ ice absorption band. The effect of finite snow depth has been investigated through a layered albedo model. The thickness of the CO₂ ice deposits increases with latitude, ranging from 0.5–1 g cm⁻² within region II to 60–80 g cm⁻² within the highest-latitude (up to 84°N) region V.Region I is at the cap edge and extends from 65°N to 72°N latitude. No CO₂ ice is present in this region, which consists of relatively large grains of water ice (20 μm), highly contaminated by dust (0.15 wt%). The adjacent region II is a narrow region [76–79°N] right at the edge of the north residual polar cap. This region is very distinct in the OMEGA image, where it appears to surround the whole residual cap. The CO₂ ice features are barely visible in these spectra, except for the strong saturated 2.7 μm band. It basically consists of a thin layer of 5-mm CO₂ ice on top of an H₂O ice layer with the same composition as region I. A third interesting region III is found all along the shoulder of the residual cap [79–81°N]. It extends over 1.5 km in altitude and over only 2° of latitude and consists of CO₂ ice with a large dust content. It is an admixture of CO₂ ice (3–4 mm), with several tens of ppm by mass of water ice and more than 2 ppt by mass of dust. The surface temperatures have been retrieved from the LWC spectra for each observation. We found an increase in the surface temperature in this region, indicating a spatial mixture of cold CO₂ ice and warmer dust/H₂O ice. Region IV is close to the top of the residual cap [81–84°N]; it is much brighter than region III, with a dust content 10 times lower than the latter. The CO₂ grain size is 3 mm and strong CO₂ ice features are present in the data, indicating a thicker CO₂ ice layer than in region II (1–2 g cm⁻²). The final region V is right at the top of the residual cap (⩾84°N). It is “pure” CO₂ ice (no dust) of 5 mm grain sizes, with 30 ppm by weight of water ice. The CO₂ ice features are very pronounced and the 2.7 μm band is saturated. The optical thickness is close to the semi-infinite limit (30–40 g cm⁻²). Assuming a snowpack density of 0.5 g cm⁻³, we get a minimum thickness of 1–2 cm for the top-layer of regions II and III, 4–10 cm for region IV, and ⩾60–80 cm thickness for region V. These values are in close agreement with several recent results for the south seasonal polar cap.These results should provide new, useful constraints in models of the Martian climate system and volatile cycles.     

Identification of C4H5, C4H4, C3H3 and CH3 radicals produced from the reaction of atomic carbon with propene: Implications for the atmospheres of Titan and giant planets and for the interstellar medium

We observed the products C₄H₅, C₄H₄, C₃H₃ and CH₃ of the C(³P) + C₃H₆ reaction using product time-of-flight spectroscopy and selective photoionization. The identified species arise from the product channels C₄H₅ + H, C₄H₄ + 2H and C₃H₃ + CH₃. Product isomers were identified via measurements of photoionization spectra and calculations of adiabatic ionization energy. Product C₄H₅ probably involves three isomers HCCCHCH₃, H₂CCCCH₃ and H₂CCCHCH₂. In contrast, products C₄H₄ and C₃H₃ involve exclusively HCCCHCH₂ and H₂CCCH, respectively. Reaction mechanisms are unraveled with crossed-beam experiments and quantum-chemical calculations. The ³P carbon atom attacks the π orbital of propene (C₃H₆) to form a cyclic complex c-H₂C(C)CHCH₃ that rapidly opens the ring to form H₂CCCHCH₃ followed by decomposition to HCCCHCH₃/H₂CCCCH₃/H₂CCCHCH₂ + H and H₂CCCH + CH₃; the corresponding branching ratios are 7:5:10:78 predicted with RRKM calculations at collision energy 4 kcal mol^?1. Nascent C₄H₅ with enough internal energy further decomposes to HCCCHCH₂ + H. Ratios of products C₄H₅, C₄H₄ and C₃H₃ are experimentally evaluated to be 17:8:75. This work provides a comprehensive look at product channels of the title reaction and gives implications for the formation of hydrocarbons in extra-terrestrial environments such as Titan and carbon-rich interstellar media. We suggest that the title reaction, hitherto excluded in any chemical networks, needs to be taken into account at least in the atmosphere of Titan and carbon-rich molecular clouds where rapid neutral–neutral reactions are dominant and carbon atoms and propene are abundant.     

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

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

Suggestion for the search of H2CC in cool cosmic objects

The transition 1₁₁ ? 1₁₀ at 4.829 GHz of formaldehyde (H₂CO) was the first one showing the anomalous absorption, i.e., the absorption against the cosmic microwave background. Anomalous absorption is an unusual phenomena. Structure of H₂CC is very similar to that of H₂CO and H₂CS. Both H₂CO and H₂CS have already been identified in a number of cosmic objects. Though H₂CC is not yet identified in the cosmic objects, we propose that H₂CC may be identified in cool cosmic objects through its transition 1₁₁ ? 1₁₀ at 4.85 GHz in anomalous absorption.     

Influence of methane concentration on the optical indices of Titan’s aerosols analogues

This work deals with the optical constant characterization of Titan aerosol analogues or “tholins” produced with the PAMPRE experimental setup and deposited as thin films onto a silicon substrate. Tholins were produced in different N₂–CH₄ gaseous mixtures to study the effect of the initial methane concentration on their optical constants. The real (n) and imaginary (k) parts of the complex refractive index were determined using the spectroscopic ellipsometry technique in the 370–1000 nm wavelength range. We found that optical constants depend strongly on the methane concentrations of the gas phase in which tholins are produced: imaginary optical index (k) decreases with initial CH₄ concentration from 2.3 × 10^?2 down to 2.7 × 10^?3 at 1000 nm wavelength, while the real optical index (n) increases from 1.48 up to 1.58 at 1000 nm wavelength. The larger absorption in the visible range of tholins produced at lower methane percentage is explained by an increase of the secondary and primary amines signature in the mid-IR absorption. Comparison with results of other tholins and data from Titan observations are presented. We found an agreement between our values obtained with 10% methane concentration, and Imanaka et al. (Imanaka, H., Khare, B.N., Elsila, J.E., Bakes, E.L.O., McKay, C.P., Cruikshank, D.P., Sugita, S., Matsui, T., Zare, R.N. [2004]. Icarus, 168, 344–366) values, in spite of the difference in the analytical method. This confirms a reliability of the optical properties of tholins prepared with various setups but with similar plasma conditions. Our comparison with Titan’s observations also raises a possible inconsistency between the mid-IR aerosol signature by VIMS and CIRS Cassini instruments and the visible Huygens-DISR derived data. The mid-IR VIMS and CIRS signatures are in agreement with an aerosol dominated by an aliphatic carbon content, whereas the important visible absorption derived from the DISR measurement seems to be incompatible with such an important aliphatic content, but more compatible with an amine-rich aerosol.     

Infrared photometric study of SDSS selected narrow line Seyfert 1 galaxies

The infrared photometric study of SDSS selected Narrow Line Seyfert 1 Galaxies (NLS1s) is presented in this paper. We have made cross-identifications for such NLS1s with 2MASS and WISE observations. Finally 992 NLS1s have 2MASS and WISE counterparts. Comparisons of NLS1s with the Broad Line Seyfert 1 (BLS1s) and Seyfert 2 galaxies are made. It is shown that from 1 µm to 5 µm NLS1s are redder than BLS1s and Seyfert 2 galaxies possibly due to the richer dust environment in NLS1 nuclei or to the orientation effect while in the longer wavelengths those three kinds of sources have quite similar behavior indicative of radiation mainly from the similar warm starburst-related dust and the related AGN dust.In addition, relations between infrared colors and related (to H_β) strengths of some important lines are also investigated. The results show that the related strengths of [FeII] 4570 Å are positively correlated with infrared colors in the 1–5 µm region, but negatively correlated with infrared colors in the 12–22 µm region; the related strength of [OIII] 5007 Å are negatively correlated with infrared colors in the 1–5 µm region, but positively correlated with infrared colors in the 12–22 µm region; the related strength of [NII]6583 Å are also negatively correlated with infrared colors in the 1–5 µm region, but positively correlated with infrared colors in the 12–22 µm region. Therefore it is indicated that the behavior of [FeII] 4570 Å is just opposed to that for [OIII] 5007 Å and [NII] 6583 Å This result may be caused by different origins of such lines.     

Circulation of the Venus upper mesosphere/lower thermosphere: Doppler wind measurements from 2001–2009 inferior conjunction,sub-millimeter CO absorption line observations

Sub-millimeter ¹²CO (346 GHz) and ¹³CO (330 GHz) line absorptions, formed within the mesospheric to lower thermospheric altitude (70–120 km) region of the Venus atmosphere, have been mapped across the nightside disk of Venus during 2001–2009 inferior conjunctions, employing the James Clerk Maxwell Telescope (JCMT). Radiative transfer analysis of these thermal line absorptions supports temperature and CO mixing profile retrievals, as described in a companion paper (Clancy et al., 2012). Here, we consider the analysis of the sharp line absorption cores of these CO spectra in terms of accurate Doppler wind profile measurements at 95–115 km altitudes versus local time (～8 pm–4 am) and latitude (～60N–60S). These Doppler wind measurements support determinations of the nightside zonal and subsolar-to-antisolar (SSAS) circulation components over a variety of timescales. The average behavior fitted from 21 retrieved maps of ¹²CO Doppler winds (obtained over hourly, daily, weekly, and interannual intervals) indicates stronger average zonal (85 m/s retrograde) versus SSAS (65 m/s) circulation at the 1 μbar pressure (108–110 km altitude) level. However, the absolute and relative magnitudes of these circulation components exhibit extreme variability over daily to weekly timescales. Furthermore, the individual Doppler wind measurements within each nightside mapping observation generally show significant deviations (20–50 m/s, averaged over 5000 km horizontal scales) from the simple zonal/SSAS solution, with distinct local time and latitudinal characters that are also time variable. These large scale residual circulations contribute 30–70% of the observed nightside Doppler winds at any given time, and may be most responsible for global variations in nightside lower thermospheric trace composition and temperatures, as coincidentally retrieved CO abundance and temperature distributions do not correlate with solution retrograde zonal and SSAS winds (see companion paper, Clancy et al., 2012). Limited comparisons of these nightside submillimeter results with dayside infrared Doppler wind measurements suggest distinct dayside versus nightside circulations, in terms of zonal winds in particular. Combined ¹²CO and ¹³CO Doppler wind mapping observations obtained since 2004 indicate that the average zonal and SSAS wind components increase by 50–100% between altitudes of 100 and 115 km. If gravity waves originating from the cloud levels are responsible for the extension of zonal winds into the thermosphere (Alexander, M.J. [1992]. Geophys. Res. Lett. 19, 2207–2210), such waves deposit substantial momentum (i.e., break) in the lower nightside thermosphere.     

Atomic oxygen on the Venus nightside: Global distribution deduced from airglow mapping

The Visible and Infra-Red Thermal Imaging Spectrometer (VIRTIS) instrument on board the Venus Express spacecraft has measured the O₂(a¹Δ) nightglow distribution at 1.27 μm in the Venus mesosphere for more than two years. Nadir observations have been used to create a statistical map of the emission on Venus nightside. It appears that the statistical 1.6 MR maximum of the emission is located around the antisolar point. Limb observations provide information on the altitude and on the shape of the emission layer. We combine nadir observations essentially covering the southern hemisphere, corrected for the thermal emission of the lower atmosphere, with limb profiles of the northern hemisphere to generate a global map of the Venus nightside emission at 1.27 μm. Given all the O₂(a¹Δ) intensity profiles, O₂(a¹Δ) and O density profiles have been calculated and three-dimensional maps of metastable molecular and atomic oxygen densities have been generated. This global O density nightside distribution improves that available from the VTS3 model, which was based on measurements made above 145 km. The O₂(a¹Δ) hemispheric average density is 2.1 × 10⁹ cm^?3, with a maximum value of 6.5 × 10⁹ cm^?3 at 99.2 km. The O density profiles have been derived from the nightglow data using CO₂ profiles from the empirical VTS3 model or from SPICAV stellar occultations. The O hemispheric average density is 1.9 × 10¹¹ cm^?3 in both cases, with a mean altitude of the peak located at 106.1 km and 103.4 km, respectively. These results tend to confirm the modeled values of 2.8 × 10¹¹ cm^?3 at 104 km and 2.0 × 10¹¹ cm^?3 at 110 km obtained by Brecht et al. [Brecht, A., Bougher, S.W., Gérard, J.-C., Parkinson, C.D., Rafkin, S., Foster, B., 2011a. J. Geophys. Res., in press] and Krasnopolsky [Krasnopolsky, V.A., 2010. Icarus 207, 17–27], respectively. Comparing the oxygen density map derived from the O₂(a¹Δ) nightglow observations, it appears that the morphology is very different and that the densities obtained in this study are about three times higher than those predicted by the VTS3 model.