The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: II. Results from a coupled dynamics-microphysics-photochemistry GCM

We present a 2D general circulation model of Titan's atmosphere, coupling axisymmetric dynamics with haze microphysics, a simplified photochemistry and eddy mixing. We develop a parameterization of latitudinal eddy mixing by barotropic waves based on a shallow-water, longitude-latitude model. The parameterization acts locally and in real time both on passive tracers and momentum. The mixing coefficient varies exponentially with a measure of the barotropic instability of the mean zonal flow. The coupled GCM approximately reproduces the Voyager temperature measurements and the latitudinal contrasts in the distributions of HCN and C₂H₂, as well as the main features of the zonal wind retrieved from the 1989 stellar occultation. Wind velocities are consistent with the observed reversal time of the North-South albedo asymmetry of 5 terrestrial years. Model results support the hypothesis of a non-uniform distribution of infrared opacity as the cause of the Voyager temperature asymmetry. Transport by the mean meridional circulation, combined with polar vortex isolation may be at the origin of the latitudinal contrasts of trace species, with eddy mixing remaining restricted to low latitudes most of the Titan year. We interpret the contrasts as a signature of non-axisymmetric motions.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: I. General properties from a horizontal shallow-water model

We present a numerical study of barotropic waves in Titan's stratosphere based on a shallow-water model. The forcing of the zonal flow by the mean meridional circulation is represented by a relaxation towards a barotropically unstable wind profile. The relaxation profile is consistent with observations and with previous results from a 3D general circulation model. The time constant of the forcing that best matches the northward eddy-transport of zonal momentum from the 3D model is τ∼5 Titan days. The eddy wind field is a zonal wavenumber-2 wave with a peak amplitude about 10% of the mean wind speed. The latitudinal transport of angular momentum by the wave tends to keep the flow close to marginal stability by carrying momentum upgradient, from the core of the jets into the low latitudes. Although the strongest eddy motions occur at the latitudes of the wind maxima, the strongest mixing takes place at the barotropically unstable regions, close to ±30° and spanning about 30° in latitude. An eddy-mixing time constant of the order of 1 Titan day is inferred within these regions, and of a few tens of days within regions of stable flow. Horizontal gradients in transient tracer fields are less than 10% of the latitudinal gradient of the meridional tracer profile. Cassini's detection of such waves could provide a direct observation of wind speeds at stratospheric levels.     

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the CN frequency at 2210 cm⁻¹ in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV spectra of the solid products formed when HCN or CO added to the BGM is similar to the UV absorption formed from the BGM alone. This result is consistent with absence of additional UV chromophores to the solid product when these mixtures are photolyzed. The following photoproducts, which were not starting materials in our photochemical studies, have been observed on Titan: acetonitrile, benzene, diacetylene, ethane, propene, propane, and propyne.     

Nature of the iogenic plasma source in Jupiter's magnetosphere: II. Near-Io distribution

Three-dimensional calculations are presented for the distribution of the iogenic plasma source that is created near Io (i.e., within ∼24 satellite radii about Io) by O and S gases located in the volume above Io's exobase (i.e., corona and escaping extended neutral clouds, designated as the “Outer Region”) and are complementary to a preceding paper for calculations on a circumplanetary scale. The instantaneous pickup ion production rates for both electron impact and charge exchange have significant radial, north-south, and orbital-plane asymmetries beginning just inside and/or beyond Io's Lagrange sphere (5.81 Io radii) and, within the Lagrange sphere, are distributed nearly symmetrically about Io and are highly peaked about Io's exobase. The spatial natures of the corresponding pickup ion density, mass loading rates, and the pickup ion conductivity, current, and magnetic field are investigated. Spatially integrated rates are calculated for the corona volume and compared to larger Outer Region circumplanetary volumes and are also compared to estimates drawn from the scientific literature (but not modeled here) of the spatially integrated rates for pickup processes in the strongly perturbed “Inner Region” below the exobase. Within the corona volume, the spatially-integrated net-mass loading rate and total (electron impact and charge exchange) mass loading rate are only a factor of ∼3 and ∼5, respectively, smaller than those estimated for the Inner Region, whereas for the whole plasma torus, the Outer Region rates are larger or comparable to those estimated for the Inner Region. The total pickup ion gyration power supplied to the whole plasma torus is estimated to be significantly less than the power radiated by the plasma torus, indicating that an additional power source, likely a circumplanetary distribution of nonthermal electrons, is present.     

Titan trace gaseous composition from CIRS at the end of the Cassini-Huygens prime mission

This paper reports on the results from an extensive study of all nadir-looking spectra acquired by Cassini/CIRS during the 44 flybys performed in the course of the nominal mission (2004-2008). With respect to the previous study (Coustenis, A., and 24 colleagues [2007]. Icarus 189, 35-62, on flybys TB-T10) we present here a significantly richer dataset with, in particular, more data at high northern and southern latitudes so that the abundances inferred here at these regions are more reliable. Our enhanced high-resolution dataset allows us to infer more precisely the chemical composition of Titan all over the disk. We also include improved spectroscopic data for some molecules and updated temperature profiles. The latitudinal distributions of all of the gaseous species are inferred. We furthermore test vertical distributions essentially for acetylene (C₂H₂) from CIRS limb-inferred data and from current General Circulation Models for Titan and compare our results on all the gaseous abundances with predictions from 1-D photochemical-radiative models to check the reliability of the chemical reactions and pathways.     

Reflectance spectra and chemical structure of Titan's tholins: Application to the analysis of Cassini-Huygens observations

Titan's tholins are used as analogs of Titan's aerosols and N-rich organic solids present on many icy surfaces. However, it is not clear whether or not they are relevant analogs, and which kind of tholins should be used among a wide set available in literature. This paper presents reflectance spectral data of two tholins selected as end-members of a series of samples covering a very wide range of continuous chemical and optical properties. These samples were formed under experimental conditions fairly consistent with Titan's stratosphere. A general framework for using these laboratory data to the analysis of spectral observation of Titan's surface or other objects is suggested. Furthermore, the study reports the first in situ unambiguous identification of aromatics compounds and evidences variations in the sp² carbon structure, which controls the absorption properties in the visible/NIR. These results also point out it is very unlikely to derive quantitative chemical information (e.g., N content, sp²/sp³ ratio) from remote sensing reflectance data.     

Corona-like atmospheric escape from KBOs: II. The behavior of aerosols

In Levi and Podolak (Levi, A., Podolak, M. [in press] Icarus) we applied the theory of coronal expansion to gas escape from a small, cold, object such as those found in the Kuiper belt. Here we extend the theory to include aerosols that are lifted off the surface by the escaping gas. Aerosols carried by the gas but still gravitationally bound, tend to be lifted to a height above the surface that is dependent on the aerosol radius, so that in steady state the variation of aerosol radius with height is well-defined. We develop an extension of Parker’s coronal flow theory to include the effect of aerosols carried along by the gas and use this to estimate the optical depth of such an atmosphere. For KBOs with CO evaporation from the surface and with radii in the range 245-334 km, line-of-site optical depths through the atmosphere can exceed one at heights of a few hundred kilometers above the surface. Such aerosol layers should be observable, and might be used to infer the flow proprieties of the escaping gas.     

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.     

Corona-like atmospheric escape from KBOs: I. Gas dynamics

We show that for low temperatures (T∼30 K) and small, but non-negligible, gravitational fields the hydrodynamic escape of gas can be treated by Parker's theory of coronal expansion [Parker, E.N., 1963. Interplanetary Dynamical Processes. Interscience Publishers, New York]. We apply this theory to gas escape from Kuiper belt objects. We derive limits on the density and radius of the bodies for which this theory is applicable, and show how the flow depends on the mean molecular weight and internal degrees of freedom of the gas molecules. We use these results to explain the CH₄ dichotomy seen on KBOs [Schaller, E.L., Brown, M.E., 2007. Astrophys. J., 659, L61-L64].     

Nature of the iogenic plasma source in Jupiter's magnetosphere: I. Circumplanetary distribution

Three-dimensional calculations are presented for the circumplanetary nature of the iogenic plasma source (pickup ions produced by electron and charge exchange processes in the plasma torus) created by O and S gases located above Io's exobase in its corona and escaping extended neutral clouds (designated as the “Outer Region”). These calculations are undertaken using neutral cloud models for O and S with realistic incomplete collisional cascade source velocity distributions and rates at Io's exobase and realistic spacetime loss processes in the plasma torus. The resulting spatial distributions for O and S about Jupiter are highly peaked at Io but extend at much lower density levels all about the planet, particularly within Io's orbit where they may play a role in the pitch angle scattering and energy loss of radially inward diffusing energetic electrons for the synchrotron radiation belts of Jupiter, in producing bite-outs in the energy distribution of energetic heavy ions near Io's orbit, and in providing a charge exchange source for energetic neutral atoms (ENAs) detected both near and far from Jupiter. For the iogenic plasma source created by these neutrals, two-dimensional distributions produced by integrating the three-dimensional information along the magnetic field lines are presented for the instantaneous values of the pickup ion rates, the total- and net-mass loading rates, the mass-per-unit-magnetic-flux source rate, the pickup conductivity, the pickup radial current, and the pickup ion power (or energy rate). On the circumplanetary spatial scale, the instantaneous iogenic plasma source is highly peaked about Io's position on its orbit around Jupiter. The degree of orbital asymmetry and its physical origin are discussed, and overall spatially integrated rates are presented. The spatially integrated net-mass loading rate is 154 kg s⁻¹ and the total (electron impact and charge exchange) mass loading rate is 275 kg s⁻¹. Rough minimum estimates are made for the spatially integrated total-mass loading rate created by the “Inner Region” (spatial region below Io's exobase) and are at least ∼1 to 2.5 times larger than that for the Outer Region. Implications of the iogenic plasma source created by the Outer Region and the Inner Region are discussed.     

Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds

Titan, Saturn's largest moon, has a thick nitrogen/methane atmosphere. The temperature and pressure conditions in Titan's atmosphere are such that the methane vapor should condense near the tropopause to form clouds. Several ground-based measurements have observed sparse cloud-like features in Titan's atmosphere, while the Cassini mission to Saturn has provided large scale images of the clouds. However, Titan's cloud formation conditions remain poorly constrained. Heterogeneous nucleation (from the vapor phase onto a solid or liquid aerosol surface) greatly enhances cloud formation relative to homogeneous nucleation. In order to elucidate the cloud formation mechanism near the tropopause, we have performed laboratory measurements of the adsorption of methane and ethane onto solid organic particles (tholins) representative of Titan's photochemical haze. We find that monolayers of methane adsorb onto tholin particles at saturation ratios less than unity. We also find that solid methane nucleates onto the adsorbed methane at a saturation ratio of S=1.07±0.008. This implies that Titan's methane clouds should form easily. This is consistent with recent measurements of the column of methane ruling out excessive methane supersaturation. In addition, we find ethane adsorbs onto tholin particles in a metastable phase prior to nucleation. However, ethane nucleation onto the adsorbed ethane occurs at a relatively high saturation ratio of S=1.36±0.08. These findings are consistent with the recent report of polar ethane clouds in Titan's lower stratosphere.     

Modeling chemical growth processes in Titan's atmosphere 2. Theoretical study of reactions between C2H and ethene, propene, 1-butene, 2-butene, isobutene, trimethylethene, and tetramethylethene

Barrierless reactions between unsaturated hydrocarbons and the ethynyl radical (C₂H) can contribute to the growth of organic particulates in the haze-forming regions of Titan's atmosphere as well as in the gas giants and in the interstellar medium. We employed a combination of quantum chemistry and statistical rate theories to characterize reactions between ground state C₂H and seven alkenes of the general structure R₁R₂C^′C^″R₃R₄ containing up to six carbons. The alkenes included ethene (C₂H₄); propene (C₃H₆); 1-butene, 2-butene, and isobutene (C₄H₈); trimethylethene (C₅H₁₀); and tetramethylethene (C₆H₁₂). Density functional theory calculations at the B3LYP/6-31 + G^∗∗ level were used to characterize the adducts, isomers, products, and the intervening transition states for the addition-elimination reactions of all seven species. A multiple-well treatment was then employed to determine the outcome distributions for the range of temperatures and pressures relevant to Titan's atmosphere, the interstellar medium, and the outer atmospheres of the gas giants. Finally, trajectory calculations using an ROMP2 potential energy surface were used to calculate kinetic rates for the ethene + C₂H reaction, where the agreement between the computed and measured values is very good. At low pressure and temperature, vinyl acetylene is a dominant product of several of the reactions, and all of the reactions yield at least one dominant product with both a double and a triple CC bond.     

Low temperature (39-298 K) kinetics study of the reactions of the C4H radical with various hydrocarbons observed in Titan's atmosphere

The reaction kinetics of the butadinyl radical, C₄H, with various hydrocarbons detected in the atmosphere of Titan (methane, ethane, propane, acetylene, ethene and methylacetylene) are studied over the temperature range of 39-298 K using the Rennes CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme) apparatus. Kinetic measurements were made using the pulsed laser photolysis—laser induced fluorescence technique. The rate coefficients, except for the reaction with methane, all show a negative temperature dependence and can be fitted with the following expressions over the temperature range of this study: ; ; , , . These expressions are not intended to be physically meaningful but rather to provide an easy way to introduce experimental results in photochemical models. They are only valid over the temperature range of the experiments. Possible channels of these reactions are discussed as well as possible consequences of these results for the production of large molecules and hazes in the atmosphere of Titan. These results should also be considered for the photochemistry of Giant Planets.     

Simulation of Titan haze formation using a photochemical flow reactor: The optical constants of the polymer

Solar UV is the principal energy source impinging the atmosphere of Titan while the energy from the electrons in Saturn's magnetosphere is less than 0.5% of the UV light. Titan haze analogs were prepared by the photolysis of a mixture of gases that simulate the composition of its atmosphere (nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene). The real (n) and imaginary (k) parts of the complex refractive index of haze analogs formed from four different gas mixtures were calculated from the spectral properties of the solid polymer in UV-visible, near infrared and infrared wavelength spectral regions. The value of n was constant at 1.6±0.1 throughout the 0.2-2.5 μm region. The variation of k with wavelength for the values derived for Titan has a lower error than the absolute values of k so the more significant comparisons are with the slopes of the k(λ) plots in the UV-VIS region. Three of the photochemical Titan haze analogs had slopes comparable to those derived for Titan from the Voyager data (Rages and Pollack, 1980, Icarus 41, 119-130; McKay and Toon, 1992, in: Proceedings of the Symposium on Titan, in: ESA SP, Vol. 338, pp. 185-190). The slopes of the k(λ) plots for haze analogs prepared by spark discharge (Khare et al., 1984, Icarus 60, 127-137) and plasma discharge (Ramirez et al., 2002, Icarus 156, 515-529) were also comparable to Titan's. These finding show that the k(λ) plots do not differentiate between different laboratory simulations of atmospheric chemistry on Titan in the UV-VIS near IR region (0.2-2.5 microns). There is a large difference between the k(λ) in the infrared between the haze analogs prepared photochemically and analogs prepared using a plasma discharges (Khare et al., 1984, Icarus 60, 127-137; Coll et al., 1999, Planet. Space Sci. 47, 1331-1340; Khare et al., 2002, Icarus 160, 172-182). The C/N ratio in the haze analog prepared by discharges is in the 2-11 range while that of the photochemical analogs is in the 18-24 range. The use of discharges and UV light for initiating the chemistry in Titan's atmosphere is discussed.     

Diagnostics of Titan's stratospheric dynamics using Cassini/CIRS data and the 2-dimensional IPSL circulation model

The dynamics of Titan's stratosphere is discussed in this study, based on a comparison between observations by the CIRS instrument on board the Cassini spacecraft, and results of the 2-dimensional circulation model developed at the Institute Pierre-Simon Laplace, available at http://www.lmd.jussieu.fr/titanDbase [Rannou, P., Lebonnois, S., Hourdin, F., Luz, D., 2005. Adv. Space Res. 36, 2194-2198]. The comparison aims at both evaluating the model's capabilities and interpreting the observations concerning: (1) dynamical and thermal structure using temperature retrievals from Cassini/CIRS and the vertical profile of zonal wind at the Huygens landing site obtained by Huygens/DWE; and (2) vertical and latitudinal profiles of stratospheric gases deduced from Cassini/CIRS data. The modeled thermal structure is similar to that inferred from observations (Cassini/CIRS and Earth-based observations). However, the upper stratosphere (above 0.05 mbar) is systematically too hot in the 2D-CM, and therefore the stratopause region is not well represented. This bias may be related to the haze structure and to misrepresented radiative effects in this region, such as the cooling effect of hydrogen cyanide (HCN). The 2D-CM produces a strong atmospheric superrotation, with zonal winds reaching 200 m s⁻¹ at high winter latitudes between 200 and 300 km altitude (0.1-1 mbar). The modeled zonal winds are in good agreement with retrieved wind fields from occultation observations, Cassini/CIRS and Huygens/DWE. Changes to the thermal structure are coupled to changes in the meridional circulation and polar vortex extension, and therefore affect chemical distributions, especially in winter polar regions. When a higher altitude haze production source is used, the resulting modeled meridional circulation is weaker and the vertical and horizontal mixing due to the polar vortex is less extended in latitude. There is an overall good agreement between modeled chemical distributions and observations in equatorial regions. The difference in observed vertical gradients of C₂H₂ and HCN may be an indicator of the relative strength of circulation and chemical loss of HCN. The negative vertical gradient of ethylene in the low stratosphere at 15° S, cannot be modeled with simple 1-dimensional models, where a strong photochemical sink in the middle stratosphere would be necessary. It is explained here by dynamical advection from the winter pole towards the equator in the low stratosphere and by the fact that ethylene does not condense. Near the winter pole (80° N), some compounds (C₄H₂, C₃H₄) exhibit an (interior) minimum in the observed abundance vertical profiles, whereas 2D-CM profiles are well mixed all along the atmospheric column. This minimum can be a diagnostic of the strength of the meridional circulation, and of the spatial extension of the winter polar vortex where strong descending motions are present. In the summer hemisphere, observed stratospheric abundances are uniform in latitude, whereas the model maintains a residual enrichment over the summer pole from the spring cell due to a secondary meridional overturning between 1 and 50 mbar, at latitudes south of 40-50° S. The strength, as well as spatial and temporal extensions of this structure are a difficulty, that may be linked to possible misrepresentation of horizontally mixing processes, due to the restricted 2-dimensional nature of the model. This restriction should also be kept in mind as a possible source of other discrepancies.     

Ozone abundance on Mars from infrared heterodyne spectra: II. Validating photochemical models

Ozone is an important observable tracer of martian photochemistry, including odd hydrogen (HO_x) species important to the chemistry and stability of the martian atmosphere. Infrared heterodyne spectroscopy with spectral resolution ?¹⁰⁶ provides the only ground-based direct access to ozone absorption features in the martian atmosphere. Ozone abundances were measured with the Goddard Infrared Heterodyne Spectrometer and the Heterodyne Instrument for Planetary Wind and Composition at the NASA Infrared Telescope Facility on Mauna Kea, Hawai'i. Retrieved total ozone column abundances from various latitudes and orbital positions (LS=40°, 74°, 102°, 115°, 202°, 208°, 291°) are compared to those predicted by the first three-dimensional gas phase photochemical model of the martian atmosphere [Lefèvre, F., Lebonnois, S., Montmessin, F., Forget, F., 2004. J. Geophys. Res. 109, doi:10.1029/2004JE002268. E07004]. Observed and modeled ozone abundances show good agreement at all latitudes at perihelion orbital positions (LS=202°, 208°, 291°). Observed low-latitude ozone abundances are significantly higher than those predicted by the model at aphelion orbital positions (LS=40°, 74°, 115°). Heterogeneous loss of odd hydrogen onto water ice cloud particles would explain the discrepancy, as clouds are observed at low latitudes around aphelion on Mars.     

The jovian anticyclone BA: III. Aerosol properties and color change

A study of the vertical cloud structure of oval BA and its red color change is presented in this third part of our complete analysis. A large interest in Jupiter’s anticyclone BA was created by its reddening that occurred between 2005 and 2006. In this work we quantify the color change in oval BA by using images taken with the Advanced Camera for Surveys (ACS) onboard the Hubble Space Telescope (HST) in six filters from the near ultraviolet (F250W) to the deep methane band in the near infrared (F892N). Reflectivity changes are noteworthy in nadir viewing geometry at the ultraviolet and blue wavelengths (F250W, F330W and F435W filters) but almost undetectable or inside error bars in the rest of filters (F550M, F658N and F892N). The observed reflectivity variations are discussed in terms of a commonly accepted vertical cloud structure model for jovian anticyclones in order to explore some causes for the color alteration. Our models of the observed reflectivity variation show that the vortex clouds did not change its vertical extension (top pressure) or its optical depth. We find that a change occurred in the absorbing properties of the particles populating the upper aerosols (single scattering albedo and imaginary refractive index). A discussion on the thermo-physical and dynamical properties of the vortex that could be in the origin of the color change is also presented.     

Binary asteroid population: 1. Angular momentum content

We compiled a list of estimated parameters of binary systems among asteroids from near-Earth to trojan orbits. In this paper, we describe the construction of the list, and we present results of our study of angular momentum content in binary asteroids. The most abundant binary population is that of close binary systems among near-Earth, Mars-crossing, and main belt asteroids that have a primary diameter of about 10 km or smaller. They have a total angular momentum very close to, but not generally exceeding, the critical limit for a single body in a gravity regime. This suggests that they formed from parent bodies spinning at the critical rate (at the gravity spin limit for asteroids in the size range) by some sort of fission or mass shedding. The Yarkovsky-O'Keefe-Radzievskii-Paddack (YORP) effect is a candidate to be the dominant source of spin-up to instability. Gravitational interactions during close approaches to the terrestrial planets cannot be a primary mechanism of formation of the binaries, but it may affect properties of the NEA part of the binary population.     

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

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