Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

Saturn's magnetospheric interaction with Titan as defined by Cassini encounters T9 and T18: New results

We present new results of Cassini's T9 flyby with complementary observations from T18. Based on Cassini plasma spectrometer (CAPS) and Cassini magnetometer (MAG), compositional evidence shows the upstream flow for both T9 and T18 appears composed of light ions (H⁺ and H₂⁺), with external pressures ∼30 times lower than that for the earlier TA flyby where heavy ions dominated the magnetospheric plasma. When describing the plasma heating and sputtering of Titan's atmosphere, T9 and T18 can be considered interactions of low magnetospheric energy input. On the other hand, T5, when heavy ion fluxes are observed to be higher than typical (i.e., TA), represents the limiting case of high magnetospheric energy input to Titan's upper atmosphere. Anisotropy estimates of the upstream flow are 1<T_⊥/T_‖<3 and the flow is perpendicular to B, indicative of local picked up ions from Titan's H and H₂ coronae extending to Titan's Hill sphere radius. Beyond this distance the corona forms a neutral torus that surrounds Saturn. The T9 flyby unexpectedly resulted in observation of two “wake” crossings referred to as Events 1 and 2. Event 2 was evidently caused by draped magnetosphere field lines, which are scavenging pickup ions from Titan's induced magnetopause boundary with outward flux ∼2×10⁶ ions/cm²/s. The composition of this out flow is dominated by H₂⁺ and H⁺ ions. Ionospheric flow away from Titan with ion flux ∼7×10⁶ ion/cm²/s is observed for Event 1. In between Events 1 and 2 are high energy field aligned flows of magnetosphere protons that may have been accelerated by the convective electric field across Titan's topside ionosphere. T18 observations are much closer to Titan than T9, allowing one to probe this type of interaction down to altitudes ∼950 km. Comparisons with previously reported hybrid simulations are made.     

Ion chemistry and N-containing molecules in Titan's upper atmosphere

High-energy photons, electrons, and ions initiate ion-neutral chemistry in Titan's upper atmosphere by ionizing the major neutral species (nitrogen and methane). The Ion and Neutral Mass Spectrometer (INMS) onboard the Cassini spacecraft performed the first composition measurements of Titan's ionosphere. INMS revealed that Titan has the most compositionally complex ionosphere in the Solar System, with roughly 50 ions at or above the detection threshold. Modeling of the ionospheric composition constrains the density of minor neutral constituents, most of which cannot be measured with any other technique. The species identified with this approach include the most complex molecules identified so far on Titan. This confirms the long-thought idea that a very rich chemistry is actually taking place in this atmosphere. However, it appears that much of the interesting chemistry occurs in the upper atmosphere rather than at lower altitudes. The species observed by INMS are probably the first intermediates in the formation of even larger molecules. As a consequence, they affect the composition of the bulk atmosphere, the composition and optical properties of the aerosols and the flux of condensable material to the surface. In this paper, we discuss the production and loss reactions for the ions and how this affects the neutral densities. We compare our results to neutral densities measured in the stratosphere by other instruments, to production yields obtained in laboratory experiments simulating Titan's chemistry and to predictions of photochemical models. We suggest neutral formation mechanisms and highlight needs for new experimental and theoretical data.     

The role of organic haze in Titan's atmospheric chemistry: II. Effect of heterogeneous reaction to the hydrogen budget and chemical composition of the atmosphere

One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C₄H₂ and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH₄ due to an episodic CH₄ release into Titan's atmosphere.     

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.     

Experimental simulation of Titan's atmosphere: Detection of ammonia and ethylene oxide

For several years now, an experimental simulation of Titan's atmosphere has been on going at LISA. A cold plasma is established in a gas mixture representative of the atmosphere of the satellite. In these experiments, more than 70 organic compounds have been identified, including the first identification in this type of experimental simulation of C₄N₂ already detected in its solid form on Titan, which suggests that the setup correctly mimics the chemistry of Titan's atmosphere.We have carried out the first experimental simulation including O-containing compounds in order to study the influence of the presence of CO on the chemical behavior of Titan's atmosphere. With the help of gas chromatography–mass spectrometry (GC–MS) and infrared spectroscopy (IRS) we can thus determine which minor species still undetected in Titan's atmosphere are likely to be present and understand the complex chemistry of the atmosphere of this satellite. Surprisingly we have identified unpredicted O-containing gaseous compounds, mainly ethylene oxide (also named oxirane, C₂H₄O). This molecule has been observed in the interstellar medium by observation in the millimeter region (Astrophys. J. 489 (1997) 553; Astron. Astrophys. 337 (1998) 275). On the contrary, the predicted O-compounds (formaldehyde and methanol) have not been identified in this experiment. Furthermore, we have identified NH₃ in the gaseous products with an initial mixture of N₂ (98%) and CH₄ (2%).The paper describes the experimental device used in this work, in particular the IRS and GC–MS techniques. We also comment the results related to the detection of the O-containing compounds and NH₃ and their implications on our knowledge of the chemistry of Titan's atmosphere and on the retrieval of the future Titan data expected from Cassini-Huygens.     

Titan's corona: The contribution of exothermic chemistry

The contribution of exothermic ion and neutral chemistry to Titan's corona is studied. The production rates for fast neutrals N₂, CH₄, H, H₂, ³CH₂, CH₃, C₂H₄, C₂H₅, C₂H₆, N(⁴S), NH, and HCN are determined using a coupled ion and neutral model of Titan's upper atmosphere. After production, the formation of the suprathermal particles is modeled using a two-stream simulation, as they travel simultaneously through a thermal mixture of N₂, CH₄, and H₂. The resulting suprathermal fluxes, hot density profiles, and energy distributions are compared to the N₂ and CH₄ INMS exospheric data presented in [De La Haye, V., Waite Jr., J.H., Johnson, R.E., Yelle, R.V., Cravens, T.E., Luhmann, J.G., Kasprzak, W.T., Gell, D.A., Magee, B., Leblanc, F., Michael, M., Jurac, S., Robertson, I.P., 2007. J. Geophys. Res., doi:10.1029/2006JA012222, in press], and are found insufficient for producing the suprathermal populations measured. Global losses of nitrogen atoms and carbon atoms in all forms due to exothermic chemistry are estimated to be and .     

Analysis of Titan's neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer measurements

In this paper we present an in-depth study of the distributions of various neutral species in Titan's upper atmosphere, between 950 and 1500 km for abundant species (N₂, CH₄, H₂) and between 950 and 1200 km for other minor species. Our analysis is based on a large sample of Cassini/INMS (Ion Neutral Mass Spectrometer) measurements in the CSN (Closed Source Neutral) mode, obtained during 15 close flybys of Titan. To untangle the overlapping cracking patterns, we adopt Singular Value Decomposition (SVD) to determine simultaneously the densities of different species. Except for N₂, CH₄, H₂ and ⁴⁰Ar (as well as their isotopes), all species present density enhancements measured during the outbound legs. This can be interpreted as a result of wall effects, which could be either adsorption/desorption of these molecules or heterogeneous surface chemistry of the associated radicals on the chamber walls. In this paper, we provide both direct inbound measurements assuming ram pressure enhancement only and abundances corrected for wall adsorption/desorption based on a simple model to reproduce the observed time behavior. Among all minor species of photochemical interest, we have firm detections of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₄H₂, C₆H₆, CH₃CN, HC₃N, C₂N₂ and NH₃ in Titan's upper atmosphere. Upper limits are given for other minor species.The globally averaged distributions of N₂, CH₄ and H₂ are each modeled with the diffusion approximation. The N₂ profile suggests an average thermospheric temperature of 151 K. The CH₄ and H₂ profiles constrain their fluxes to be and , referred to Titan's surface. Both fluxes are significantly higher than the Jeans escape values. The INMS data also suggest horizontal/diurnal variations of temperature and neutral gas distribution in Titan's thermosphere. The equatorial region, the ramside, as well as the nightside hemisphere of Titan appear to be warmer and present some evidence for the depletion of light species such as CH₄. Meridional variations of some heavy species are also observed, with a trend of depletion toward the north pole. Though some of the above variations might be interpreted by either the solar-driven models or auroral-driven models, a physical scenario that reconciles all the observed horizontal/diurnal variations in a consistent way is still missing. With a careful evaluation of the effect of restricted sampling, some of the features shown in the INMS data are more likely to be observational biases.     

Model-data comparisons for Titan's nightside ionosphere

Solar and X-ray radiation and energetic plasma from Saturn's magnetosphere interact with the upper atmosphere producing an ionosphere at Titan. The highly coupled ionosphere and upper atmosphere system mediates the interaction between Titan and the external environment. A model of Titan's nightside ionosphere will be described and the results compared with data from the Ion and Neutral Mass Spectrometer (INMS) and the Langmuir probe (LP) part of the Radio and Plasma Wave (RPWS) experiment for the T5 and T21 nightside encounters of the Cassini Orbiter with Titan. Electron impact ionization associated with the precipitation of magnetospheric electrons into the upper atmosphere is assumed to be the source of the nightside ionosphere, at least for altitudes above 1000 km. Magnetospheric electron fluxes measured by the Cassini electron spectrometer (CAPS ELS) are used as an input for the model. The model is used to interpret the observed composition and structure of the T5 and T21 ionospheres. The densities of many ion species (e.g., CH⁺₅ and C₂H⁺₅) measured during T5 exhibit temporal and/or spatial variations apparently associated with variations in the fluxes of energetic electrons that precipitate into the atmosphere from Saturn's magnetosphere.     

Ejection of nitrogen from Titan's atmosphere by magnetospheric ions and pick-up ions

A 3-D Monte Carlo model is used to describe the ejection of N and N₂ from Titan due to the interaction of Saturn's magnetospheric N⁺ ions and molecular pick-up ions with its N₂ atmosphere. Based on estimates of the ion flux into Titan's corona, atmospheric sputtering is an important source of both atomic and molecular nitrogen for the neutral torus and plasma in Saturn's outer magnetosphere, a region now being studied by the Cassini spacecraft.     

Temperature dependence of HC3N,C6H2, and C4N2 mid-UV absorption coefficients. Application to the interpretation of Titan's atmospheric spectra

Three organic compounds (HC₃N, C₆H₂, and C₄N₂) relevant of Titan's atmosphere have been studied within the framework of the SIPAT (Spectroscopie UV d'Intérêt Prébiologique dans l'Atmosphère de Titan) program. Since this facility is still unable to reach the very low temperatures (170 K) of Titan's high atmosphere, spectra have to be obtained at several absorption-cell temperatures, and the data extrapolated towards lower temperatures. Previously published HC₃N and C₆H₂ absorption coefficient data are reviewed, while new spectroscopic data are presented on C₄N₂. Integrated intensity calculations over the vibrational bands are performed apart from the background continuum. Thus, only the band contrast is considered here. While, the temperature dependence of the hot-band integrated intensity follows a Boltzmann distribution, we have enhanced the fit through an empirical parametrisation to account for the observed temperature dependence of the C₄N₂ and HC₃N absorption coefficients, and to extrapolate those data to the low temperature conditions of Titan's high atmosphere. Finally, we discuss the implications of the results to possible detection by remote sensing observations of these minor compounds in Titan's atmosphere.     

Negative ion chemistry in Titan's upper atmosphere

The Electron Spectrometer (ELS), one of the sensors making up the Cassini Plasma Spectrometer (CAPS) revealed the existence of numerous negative ions in Titan's upper atmosphere. The observations at closest approach (∼1000 km) show evidence for negatively charged ions up to ∼10,000 amu/q, as well as two distinct peaks at 22±4 and 44±8 amu/q, and maybe a third one at 82±14 amu/q. We present the first ionospheric model of Titan including negative ion chemistry. We find that dissociative electron attachment to neutral molecules (mostly HCN) initiates the formation of negative ions. The negative charge is then transferred to more acidic molecules such as HC₃N, HC₅N or C₄H₂. Loss occurs through associative detachment with radicals (H and CH₃). We attribute the three low mass peaks observed by ELS to CN⁻, C₃N⁻/C₄H⁻ and C₅N⁻. These species are the first intermediates in the formation of the even larger negative ions observed by ELS, which are most likely the precursors to the aerosols observed at lower altitudes.     

Complex Refractive Index of Titan's Aerosol Analogues in the 200-900 nm Domain

The main gas-phase constituents of Titan's upper atmosphere, N₂ and CH₄, are photolyzed and radiolyzed by solar photons and magnetospheric electrons, respectively. The primary products of these chemical interactions evolve to heavier organic compounds that are likely to associate into the particles of haze layers that hide Titan's surface. The different theories and models that have been put forward to explain the characteristics and properties of the haze composites require a knowledge of their optical properties, which are determined by the complex refractive index. We present a new set of values for refractive index n and extinction coefficient k calculated directly from the transmittance and reflectance curves exhibited by a laboratory analogue of Titan's aerosols in the 200-900 nm range. Improvements in the aerosol analogue quality have been made. The effects of variables such as the uncertainty in sample thickness, aerosol porosity, and amount of scattered light on the final n and k values are assessed and discussed. Within the studied wavelength domain, n varies from 1.53 to 1.68 and k varies from 2.62×10⁻⁴ to 2.87×10⁻². These final n and k values should be considered as a new reference to modelers who compute the properties of Titan's aerosols in trying to explain the atmospheric dynamics and surface characteristics.     

Impact of electron chemistry on the structure and composition of Io's atmosphere

Two-dimensional model calculations (altitude and solar zenith angle) are performed to investigate the impact of electron chemistry on the composition and structure of Io's atmosphere. The calculations are based upon the model of Wong and Smyth (2000, Icarus 146, 60-74) for Io's SO₂ sublimation atmosphere with the addition of new electron chemistry, where the interactions of the electrons and neutrals are treated in a simple fashion. The model calculations are presented for Io's atmosphere at western elongation (dusk ansa) for both a low-density case (subsolar temperature of 113 K) and a high-density case (subsolar temperature of 120 K). The impact of electron-neutral chemistry on the composition and structure of Io's atmosphere is confined primarily to an interaction layer. The penetration depth of the interaction layer is limited to high altitudes in the thicker dayside atmosphere but reaches the surface in the thinner dayside and/or nightside atmosphere at larger solar zenith angles. Within most of the thicker dayside atmosphere, the column density of SO₂ is not significantly altered by electrons, but in the interaction layer all number densities are significantly altered: SO₂ is reduced, O, SO, S, and O₂ are greatly enhanced, and O, SO, and S become comparable to SO₂ at high altitudes. For the thinner nightside atmosphere, the species number densities are dramatically altered: SO₂ is drastically reduced to the least abundant species of the SO₂ family, SO and O₂ are significantly reduced at all altitudes, and O and S are dramatically enhanced and become the dominant species at all altitudes except near the surface. The interaction layer also defines the location of the emission layer for neutrals excited by electron impact and hence determines the fraction of the total neutral column density that is visible in remote observation. Electron chemistry may also impact the ratio of the equatorial to polar SO₂ column density deduced from Lyman-α images and the north-south alternating and System III longitude-dependent asymmetry observed in polar O and S emissions.     

A tidal explanation for the Titan haze layers

Though Titan is in synchronous rotation around Saturn, it experiences gravitational tides as a consequence of its eccentric orbit. It is proposed that the vertical transport of aerosols by these tides produces the haze layers in Titan's upper atmosphere. Analysis shows that the zonal winds in Titan's superrotating atmosphere have a profound influence on which tidal components are effective in establishing the multiple detached-haze layers. If the Huygens Doppler winds are representative of the equatorial global superrotation, then the westward propagating s=2 mode is the responsible tidal component even though its forcing is significantly weaker than that of the s=0 and eastward s=2 components. The eastward s=2 tidal mode is eliminated by critical levels while the s=0 mode is viscously damped in the strong high altitude winds. At polar latitudes, however, the gravest s=0 mode is the one most likely to produce layering. It is also suggested that the atmospheric gravitational tides could be responsible for decelerating the superrotating atmosphere as seen in the Huygens Doppler wind velocity profile at about 80 km altitude.     

HST spectral imaging of Titan's haze and methane profile between 0.6 and 1 μm during the 2000 opposition

We report on the analysis of high spatial resolution visible to near-infrared spectral images of Titan at Ls=240° in November 2000, obtained with the Space Telescope Imaging Spectrograph instrument on board the Hubble Space Telescope as part of program GO-8580. We employ a radiative transfer fractal particle aerosol model with a Bayesian parameter estimation routine that computes Titan's absolute reflectivity per pixel for 122 wavelengths by modeling the vertical distribution of the lower atmosphere haze and tropospheric methane. Analysis of these data suggests that Titan's haze concentration in the lower atmosphere varies in strength with latitude. We find Titan's tropospheric methane profile to be fairly consistent with latitude and longitude, and we find evidence for local areas of a CH₄-N₂ binary saturation in Titan's troposphere. Our results suggest that a methane and haze profile at one location on Titan would not be representative of global conditions.     

PAMPRE: A dusty plasma experiment for Titan's tholins production and study

Organic aerosols play a significant role in the properties and evolution of Titan's atmosphere. But our knowledge of them and their physico-chemical mechanisms of formation and evolution are currently limited to a few data obtained by Titan observations from the Earth or from space probes. For this reason, laboratory experiments are developed to simulate the atmospheric chemistry and produce analogues of these aerosols in order to understand better their properties and how they are formed. The plasma discharges are the most efficient devices for the production of such analogues. However, the existing plasmas simulations introduce experimental biases compared with the conditions of aerosols production in Titan's atmosphere: chemistry is induced by electrons instead of photons; the solid analogues are produced and deposited on solid surfaces; direct analysis of the particles inside the reactive chamber is not easy. In order to avoid some of these experimental problems, we have developed another method of production of Titan's aerosols analogues. It is based on a capacitively coupled radio-frequency (RF) cold plasma system at low pressure in a N₂-CH₄ gaseous mixture. In this plasma, solid particles produced from the gas phase are in levitation, thus preventing any wall effect on their production, and allowing the study of the formation and growth of the particles directly in the plasma. Moreover, the electron energy distribution of this plasma can be compared with the solar spectrum. This article describes the RF plasma experiment and presents the first results obtained with an initial N₂-CH₄ (90:10) gaseous mixture which produced our first studied analogues of Titan's aerosols.     

Ionospheric warming by neutral winds

The effect of frictional heating by means of neutral winds on the ion and electron temperature in the undisturbed ionosphere is studied theoretically by solving a system of basic ionospheric and atmospheric equations. The study shows that both the electron and ion temperatures are increased in the night-time ionosphere through friction. In the region between 150 and 200 km T_i may exceed T₆ by as much as 130°. The increase of T_i due to friction amounts to about 100–200°, depending on the atmospheric model employed in calculating the neutral wind velocity. It is illustrated that frictional heating may be very important for the determination of the neutral temperature from measured ion temperature values.     

Laboratory experiments of Titan tholin formed in cold plasma at various pressures: implications for nitrogen-containing polycyclic aromatic compounds in Titan haze

Titan, the largest satellite of Saturn, has a thick nitrogen/methane atmosphere with a thick global organic haze. A laboratory analogue of Titan's haze, called tholin, was formed in an inductively coupled plasma from nitrogen/methane=90/10 gas mixture at various pressures ranging from 13 to 2300 Pa. Chemical and optical properties of the resulting tholin depend on the deposition pressure in cold plasma. Structural analyses by IR and UV/VIS spectroscopy, microprobe laser desorption/ionization mass spectrometry, and Raman spectroscopy suggest that larger amounts of aromatic ring structures with larger cluster size are formed at lower pressures (13 and 26 Pa) than at higher pressures (160 and 2300 Pa). Nitrogen is more likely to incorporate into carbon networks in tholins formed at lower pressures, while nitrogen is bonded as terminal groups at higher pressures. Elemental analysis reveals that the carbon/nitrogen ratio in tholins increases from 1.5-2 at lower pressures to 3 at 2300 Pa. The increase in the aromatic compounds and the decrease in C/N ratio in tholin formed at low pressures indicate the presence of the nitrogen-containing polycyclic aromatic compounds in tholin formed at low pressures. Tholin formed at high pressure (2300 Pa) consists of a polymer-like branched chain structure terminated with CH₃, NH₂, and CN with few aromatic compounds. Reddish-brown tholin films formed at low pressures (13-26 Pa) shows stronger absorptions (almost 10 times larger k-value) in the UV/VIS range than the yellowish tholin films formed at high pressures (160 and 2300 Pa). The tholins formed at low pressures may be better representations of Titan's haze than those formed at high pressures, because the optical properties of tholin formed at low pressures agree well with that of Khare et al. (1984a, Icarus 60, 127-137), which have been shown to account for Titan's observed geometric albedo. Thus, the nitrogen-containing polycyclic aromatic compounds we find in tholin formed at low pressure may be present in Titan's haze. These aromatic compounds may have a significant influence on the thermal structure and complex organic chemistry in Titan's atmosphere, because they are efficient absorbers of UV radiation and efficient charge exchange intermediaries. Our results also indicate that the haze layers at various altitudes might have different chemical and optical properties.     

Solar activity variations of thermospheric temperatures on Mars and a problem of CO in the lower atmosphere

Long-term MGS drag density observations at 390 km reveal variations of the density with season L_S (by a factor of 2) and solar activity index F_10.7 (by a factor of 3 for F_10.7 = 40-100). According to Forbes et al. (Forbes, J.M., Lemoine, F.G., Bruinsma, S.L., Smith, M.D., Zhang, X. [2008]. Geophys. Res. Lett. 35, L01201, doi:10.1029/2007GL031904), the variation with F_10.7 reflects variations of the exospheric temperature from 192 to 284 K. However, the derived temperature range corresponds to variation of the density at 390 km by a factor of 8, far above the observed factor of 3. The recent thermospheric GCMs agree with the derived temperatures but do not prove their adequacy to the MGS densities at 390 km. A model used by Forbes et al. neglects effects of eddy diffusion, chemistry and escape on species densities above 138 km. We have made a 1D-model of neutral and ion composition at 80-400 km that treats selfconsistently chemistry and transport of species with F_10.7, T_∞, and [CO₂]_80 km as input parameters. Applying this model to the MGS densities at 390 km, we find variation of T_∞ from 240 to 280 K for F_10.7 = 40 and 100, respectively. The results are compared with other observations and models. Temperatures from some observations and the latest models disagree with the MGS densities at low and mean solar activity. Linear fits to the exospheric temperatures are T_∞ = 122 + 2.17F_10.7 for the observations, T_∞ = 131 + 1.46F_10.7 for the latest models, and T_∞ = 233 + 0.54F_10.7 for the MGS densities at 390 km. Maybe the observed MGS densities are overestimated near solar minimum when they are low and difficult to measure. Seasonal variations of Mars’ thermosphere corrected for the varying heliocentric distance are mostly due to the density variations in the lower and middle atmosphere and weakly affect thermospheric temperature. Nonthermal escape processes for H, D, H₂, HD, and He are calculated for the solar minimum and maximum conditions.Another problem considered here refers to Mars global photochemistry in the lower and middle atmosphere. The models gave too low abundances of CO, smaller by an order of magnitude than those observed. Our current work shows that modifications in the boundary conditions proposed by Zahnle et al. (Zahnle, K., Haberle, R.M., Catling, D.C., Kasting, J.F. [2008]. J. Geophys. Res. 113, E11004, doi:10.1029/2008JE003160) are reasonable but do not help to solve the problem.