Carbon isotopic enrichment in Titan's tholins? Implications for Titan's aerosols

Since the discovery of the main composition of Titan's atmosphere, many laboratory experiments have been carried out to reproduce its chemical evolution, particularly the formation of organic haze particles found throughout this atmosphere. Some of these simulations have produced solid products—referred to as Titan's tholins—that are assumed to have properties similar to those of Titan's aerosols. In the present work, we focus on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan's tholins. Initial ¹²C/¹³C isotopic ratios measured on tholins made in the laboratory using cold plasma discharges are presented. Measurements of isotopic enhancement in ¹³C (δ¹³C), both on tholins and on the initial gas mixture (N₂:CH₄ (98:2)) used to produce them do not show any clear deficit or enrichment in ¹³C relative to ¹²C in the lab-made tholins compared to the initial gas mixture. Preliminary data recovered from the Aerosol Collector Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan's aerosols may also be exempt of carbon isotopic enrichment. This observation creates possibilities for deeper analysis of ACP experiment data.     

The distribution of Titan's high-altitude (out to ∼50,000 km) exosphere from energetic neutral atom (ENA) measurements by Cassini/INCA

We report observations of Titan's high-altitude exosphere detected out to about 50,000 km altitude. The observations were made by the Ion Neutral Camera (INCA) on board the Cassini spacecraft. INCA detects energetic neutral atoms (ENA) that are formed when the ambient magnetospheric ions charge exchange with Titan's neutral atmosphere and exosphere. We find that Titan's exospheric H₂ distribution follows closely a full Chamberlain distribution including ballistic, escaping and satellite distributions. As expected, neutral densities are dominated by a satellite distribution above about 10,000 km. The maximum detectable extent of the exosphere (～50,000 km) coincides with the radius of the Hill sphere of gravitational influence from Saturn. While we find no direct indications of a neutral Titan torus with densities greater than about 1000 cm^?3, we observe interesting asymmetries in the distribution that warrants further investigation. Based on these findings we compute the average precipitating ENA flux to be about 5×10⁶ keV/(cm² s), or 8×10^?3 erg/(cm² s), which is directly comparable to that of precipitating energetic ions (Sittler, et al., 2009) and slightly higher than that of solar EUV (Tobiska, 2004). Thus, the energy deposited by precipitating ENAs must also be taken into consideration when studying the energy balance of Titan's thermosphere.     

The distribution of hydrocarbons in Titan's atmosphere: An evolutionary algorithm-based model

We propose a new approach to study the chemical complexity of Titan's atmosphere. We have developed an evolutionary algorithm-based model that simulates the evolution of interacting elements with different valences. This abstract model mimics a C–H–O–N system that might get an insight into the general properties of the chemistry of Titan's atmosphere. Comparison with detailed models like photochemical models is discussed to evaluate limitations and benefits of each approach. Comparison with observations suggests that Titan's atmosphere might self-organize to produce hydrocarbons with distributions that follow a power-law relation. If confirmed, this property makes possible some prediction about the abundance of heavy hydrocarbons in the atmosphere of Titan.     

Ionospheric conditions

A general analysis of ionospheric conditions has been made in the light of possible ionic reactions occurring in the upper atmosphere. Data obtained on various parameters, such as ionic production and recombination, show that precise knowledge of the spectral distribution of solar radiation is needed and that other experimental determinations on dissociative recombinations are required.

The ionic complexity of the ionosphere is underlined by describing how the atomic ions O⁺ and N⁺ react with N₂, O₂ and NO molecules. The behavior of the molecular ions N⁺₂, O⁺₂and NO⁺depends on a group of simultaneous processes involving charge transfers and ionatom interchanges which are more important than dissociative recombinations. The altitude distribution of ions is exemplified by discussing the relative importance of various loss coefficients in the D-, E- and F-regions. It is seen that molecular nitrogen ions are subject to important charge transfer processes, that nitric oxide ions are always final products destroyed only by dissociative recombination. Additionally, the entire production of atomic oxygen ions is related to the photoionization of molecular nitrogen. Some information is also given on possible anomalies in the ratio of O⁺₂ and NO⁺ densities in the lower ionosphere. From the lack of sufficient experimental information on ionic processes it is shown that a precise analysis of ionospheric behavior remains highly speculative.     

Jovian ionospheric models

This paper reports results obtained on ionosphere formation in the Jovian upper atmosphere with special reference to some of the recently available reaction rates, and to recent models of the Jovian neutral atmosphere based on the possibility of a warmer mesopause. We find that the role of the hypothetical radiative association of H⁺ to H₂ to form H₃⁺, as brought to light in our earlier study, is still important, even with a reaction rate as low as 10^?15 cm³sec^?1. In the lower regions of the ionosphere three-body processes leading to the formation of H₃⁺ and H₅⁺ ions, which have very fast dissociative recombination rates, produce a dramatic reduction in the electron density. When no radiative association takes place, and the H⁺ ions are lost by radiative recombination alone, we confirm that the photochemical equilibrium profile is also the diffusive equilibrium profile. However, with collisional-radiative recombination, whose rate becomes altitude-dependent, diffusion tends to bring about some redistribution of the ionization. Inclusion of radiative association enhances the role of diffusion. In this case, diffusion brings about all the expected changes. In particular, the differences in the electron density profile, originated in the lower-middle ionosphere by radiative association, are propagated up to all higher altitudes by diffusion. The rate constant of radiative association is, however, unknown. It is hoped that the critical importance of this reaction for the Jovian ionosphere will be an incentive towards a careful laboratory determination of its rate coefficient. In the older models of the Jovian ionosphere the major ions were H⁺ which were lost only by pure radiative recombination. This led to high electron densities and practically no diurnal change. In contrast, our new models have relatively much smaller electron densities, especially in lower regions, and may be susceptible to significant diurnal variation.     

Photochemical kinetics uncertainties in modeling Titan's atmosphere: First consequences

Uncertainties carried by the different kinetic parameters included in photochemical models of planetary atmospheres have rarely been considered even if they are supposed to be contributing mostly to the inconsistencies between observations and computed predictions. In this paper, we report the first detailed analysis of the propagation of uncertainties carried by the reaction rate coefficients included in an up-to-date photochemical model of Titan's atmosphere. Monte Carlo calculations performed on these reaction rate coefficients have been used to introduce their uncertainties and to investigate their significance on the photochemical modeling of Titan's atmosphere. Crude approximations in the implemented physical processes have been adopted to limit the number of free parameters. This allows us to pinpoint specifically the importance of chemical processes uncertainties in Titan's photochemical models and to evaluate their chemical robustness. First implications of this preliminary study related to purely chemical rate coefficient uncertainties are discussed. They are important enough to question indeed any comparisons between theoretical models with observations as well as any potential conclusions subsequently inferred. Since the latest missions, such as Cassini–Huygens, are likely to induce an ever-increasing interest for such kind of comparing studies, our conclusions show that it is crucial to reform the way we think of, and use, current photochemical models to understand the processes occurring in the atmospheres of the outer Solar System.     

Stochastic models of hot planetary and satellite coronas: A photochemical source of hot oxygen in the upper atmosphere of Mars

The processes of the kinetics and transport of hot oxygen atoms in the upper atmosphere of Mars are studied. A reaction of dissociative recombination of the main ionospheric ion O ₂ ⁺ with thermal electrons is considered as a photochemical source of suprathermal oxygen atoms. Oxygen atoms are formed in the dissociative recombination reaction with an excess of kinetic energy of about 0.4–4 eV and lose that energy in elastic and inelastic collisions with the ambient thermal atmospheric gas. The altitude distributions of the concentrations of neutral and ionized components, as well as their temperatures, were taken from Krasnopolsky (2002). Unlike the models published earlier, detailed calculations of the formation, collisional kinetics, and transport of suprathermal oxygen atoms in the thermosphere-exosphere transition region of the upper atmosphere of Mars have been made for the first time. For this, we used a stochastic model of the formation of a hot planetary corona (Shematovich, 2004). It has been shown that the considered photochemical source of suprathermal oxygen leads to the formation of the hot corona and to higher nonthermal losses of oxygen from the upper atmosphere of Mars due to escape fluxes. The detailed energy spectra of the fluxes of suprathermal atomic oxygen were calculated for the thermosphere-exosphere transition region of the Martian atmosphere.Translated from Astronomicheskii Vestnik, Vol. 39, No. 1, 2005, pp. 26–37.Original Russian Text Copyright © 2005 by Krestyanikova, Shematovich.     

Quantitative Analysis of H2OComa Images Using a Multiscale MHD Model with Detailed Ion Chemistry

The observation of ions created by ionization of cometary gas, either by ground-based observations or byin situmeasurements can give us useful information about the gas production and composition of comets. However, due to the interaction of ions with the magnetized solar wind and their high chemical reactivity, it is not possible to relate measured ion densities (or column densities) directly to the parent gas densities. In order to quantitatively analyze measured ion abundances in cometary comae it is necessary to understand their dynamics and chemistry. We have developed a detailed ion–chemical network of cometary atmospheres. We include production of ions by photo- and electron impact-ionization of a background neutral atmosphere, charge exchange of solar wind ions with cometary atoms/molecules, reactions between ions and molecules, and dissociative recombination of molecular ions with thermal electrons. By combining the ion–chemical network with the three-dimensional plasma flow as computed by a new fully three-dimensional MHD model of cometary plasma environments (Gombosiet al.1996) we are able to compute the density of the major cometary ions everywhere in the coma. The input parameters for our model are the solar wind conditions (density, speed, temperature, magnetic field) and the composition and production rate of the gas. We applied our model to Comet P/Halley in early March 1986, for which the input parameters are reasonably well known. We compare the resulting column density of H₂O⁺with ground-based observations of H₂O⁺from DiSantiet al.(1990). The results of our model are in good agreement with both the spatial distribution and the absolute abundance of H₂O⁺and with their variations with the changing overall water production rate between two days. The results are encouraging that it will be possible to obtain production rates of neutral cometary constituents from observations of their ion products.     

Ionization chemistry in H<Subscript>2</Subscript>O-dominated atmospheres of icy moons

The processes of the formation and dynamics of tenuous gaseous envelopes of icy moons in giant-planet systems are considered. Tenuous exospheres with relatively dense surface layers are likely to form around more massive icy satellites, such as, for example, the Galilean satellites Europa and Ganymede in the Jovian system. Escaping exospheres are formed in the case of low-mass icy moons, as happens for the icy satellite Enceladus in the Saturnian system. The main parent component of such gaseous envelopes is water vapor, which enters into the atmosphere as a result of thermal degassing processes, nonthermal radiolysis, and other active processes and phenomena on the icy surface of a satellite. A numerical kinetic model has been developed to study on a molecular level the processes of the formation, chemical evolution, and dynamics of tenuous gaseous envelopes dominated mainly by H₂O. The ionization processes in such tenuous gaseous envelopes are caused by solar ultraviolet (UV) radiation and solar-wind and/or magnetospheric plasma. The primary processes when ultraviolet solar photons and plasma electrons affect the tenuous gas of the H₂O-dominated atmosphere are responsible for the chemical diversity of the gaseous envelopes of icy moons. Ionization chemistry, including ion-molecular reactions, dissociative recombination of molecular ions, and the reactions of the charge exchange with magnetospheric ions, is important for the formation of chemical diversity in gaseous envelopes of icy satellites. The model considered in the study was used to numerically simulate the formation and development of chemical diversity in the tenuous gaseous envelope of Enceladus. The numerical results were compared to the direct Cassini measurements during its close flyby near Enceladus.     

Radiocarbon on Titan

Abstract— We explore the likely production and fate of ¹⁴C in the thick nitrogen atmosphere of Saturn's moon Titan and investigate the constraints that measurements of ¹⁴C might place on Titan's photochemical, atmospheric transport and surface‐atmosphere interaction processes. Titan's atmosphere is thick enough that cosmic‐ray flux limits the production of ¹⁴C: absence of a strong magnetic field and the increased distance from the Sun suggest production rates of ?9 atom/cm²/s, ?4x higher than Earth. The fate and detectability of ¹⁴C depends on the chemical species into which it is incorporated: as methane it would be hopelessly diluted even in only the atmosphere. However, in the more likely case that the ¹⁴C attaches to the haze that rains out onto the surface (as tholin, HCN or acetylene and their polymers), haze in the atmosphere or recently deposited on the surface would be quite radioactive. Such radioactivity may lead to a significant enhancement in the electrical conductivity of the atmosphere which will be measured by the Huygens probe. Measurements with simple detectors on future missions could place useful constraints on the mass deposition rates of photochemical material on the surface and identify locations where surface deposits of such material are “freshest”.     

Measurements of positive ion conversion and removal reactions relating to the Jovian ionosphere

Measured rates are presented for the reaction of He⁺ ions with H₂ (and D₂) molecules to form H⁺, H₂⁺, and HeH⁺ ions, as well as for the subsequent reactions of H⁺ and HeH⁺ ions with H₂ to form H₃⁺. The neutralization of H₃⁺ (and H₅⁺) ions by dissociative recombination with electrons is shown to be fast. The reaction He⁺ + H₂ is slow (k = 1.1 × 10^?13 cm³/sec at300°K) and produces principally H⁺ by the dissociative charge transfer branch. It is concluded that there may be a serious bottleneck in the conversion of two of the primary ions of the upper Jovian ionosphere, H⁺ and He⁺ (which recombine slowly), to the rapidly recombining H₃⁺ ion (α[H₃⁺]?3.4 × 10^?7 cm³/sec at 150°K).     

Short-term variability of Jupiter’s extended sodium nebula

Ground-based optical observations of D₁ and D₂ line emissions from Jupiter’s sodium nebula, which extend over several hundreds of jovian radii, were carried out at Mt. Haleakala, Maui, Hawaii using a wide field filter imager from May 19 to June 21, 2007. During this observation, the east-west asymmetry of the nebula with respect to the Io’s orbital motion was clearly identified. Particularly, the D₁+D₂ brightness on the western side of Jupiter is strongly controlled by the Io phase angle. The following scenario was developed to explain this phenomenon as follows: First, more ionospheric ions like NaX⁺, which are thought to produce fast neutral sodium atoms due to a dissociative recombination process, are expected to exist in Io’s dayside hemisphere rather than in the nightside one. Second, it is expected that more NaX⁺ ionospheric ions are picked up by the jovian co-rotating magnetic field when Io’s leading hemisphere is illuminated by the Sun. Third, the sodium atom ejection rate varies with respect to Io’s orbital position as a result of the first two points. Model simulations were performed using this scenario. The model results were consistent with the observation results, suggesting that Io’s ionosphere is expected to be controlled by solar radiation just like Earth.     

Coupled ion and neutral rotating model of Titan's upper atmosphere

A one-dimensional composition model of Titan's upper atmosphere is constructed, coupling 36 neutral species and 47 ions. Energy inputs from the Sun and from Saturn's magnetosphere and updated temperature and eddy coefficient parameters are taken into account. A rotating technique at constant latitude and varying local-time is proposed to account for the diurnal variation of solar inputs. The contributions of photodissocation, neutral chemistry, ion-neutral chemistry, and electron recombination to neutral production are presented as a function of altitude and local time. Local time-dependent mixing ratio and density profiles are presented in the context of the TA and T₅ Cassini data and are compared in detail to previous models. An independent and simplified ion and neutral scheme (19-species) is also proposed for future 3D-purposes. The model results demonstrate that a complete understanding of the chemistry of Titan's upper atmosphere requires an understanding of the coupled ion and neutral chemistry. In particular, the ionospheric chemistry makes significant contributions to production rates of several important neutral species.     

Estimated impact shock production of N2 and organic compounds on early Titan

Bombardment of Titan by Uranus-Neptune planetesimals and/or fragments of a disrupted Hyperion progenitor supplied more than enough energy to drive vigorous atmospheric shock chemistry. Chemical equilibrium modeling of the shock products in simulated atmospheres indicates that impact energy has produced large amounts of N₂ and organic compounds over Titan's history. The mole fraction of organic compounds in the shocked gas mixture (T = 1200−2500°K, P = 10⁻¹−10³bar) reaches a maximum of approximately 3% in a current Titan mixture and 12% in a primordial CH₄, NH₃-rich mixture. Atmospheric water mixing ratio controls the organic yield in shock reactions, but its limiting effect may have been reduced by cold-trapping of water in a cooling atmosphere. Kinetic inhibition of graphite formation in the shocked gas enhanced the yield of radicals and organic. The resulting mixture of carbonaceous soot and condensed hydrocarbons subsequently settled onto the surface; the depth of the generated layer was on the order of hundreds of meters. Impact shock energy was capable of converting massive amounts of NH₃ to N₂ early in Titan history—over twice the present atmospheric and 1.5 times the total ocean-atmospheric inventory of N₂. Shock conversion of NH₃ into N₂ bypasses the difficulties of other schemes of N₂ production and may have been of singular importance in Titan's atmospheric evolution.     

Products of meteoric metal ion chemistry within planetary atmospheres. 1. Mg at Titan

We report results of quantum chemical calculations of Mg⁺/ligand bond dissociation energies involving ligands identified as major constituents of Titan's upper atmosphere. Trends identified in these results allow elucidation of the important bimolecular and termolecular reactions of Mg⁺, and of simple molecular ions containing Mg⁺, arising from meteoric infall into Titan's atmosphere. Our study highlights, and includes calculated rate coefficients for, crucial ligand-switching and ligand-stripping reactions which ensure that a dynamic equilibrium exists between atomic and molecular ions of Mg⁺. Neutralization of ionized meteoric Mg is expected to produce the radical MgNC in high yield. The highly polar MgNC radical should provide an excellent nucleation site for condensation of polar (e.g., HCN, CH₃CN, and HC₃N) and highly unsaturated (e.g., C₂H₂, C₄H₂, and C₂N₂) neutrals at comparatively high altitude, leading to precipitation of Mg-doped tholin-like material. The implications for Titan's prebiotic chemical evolution, of the surface deposition of such material (which may feasibly contain magnesium porphyrins, or other bioactive Mg-containing complexes) remain to be assessed.     

Production of hot nitrogen atoms in the martian thermosphere

The energy and altitude distributions for nitrogen atoms produced from photodissociation of N₂ and dissociative recombination of N⁺₂ have been computed for the low and high solar activity martian thermospheres. We find that the fraction of nitrogen atoms with E>Eesc at the exobase is ∼2.5% for photodissociation as compared to ∼22.6% for dissociative recombination. However, the peak magnitudes of the production rate profiles for dissociative recombination are a factor of ∼1000 and ∼200 times smaller than those of photodissociation at low and high solar activities, respectively. Thus, our findings suggest that photodissociation of N₂ is the dominant escape mechanism for atomic nitrogen for both the low and high solar activity martian thermospheres. The general consensus in the field prior to these research results was that dissociative recombination of N⁺₂ was the main escape mechanism. We find that it is the dissociation of N₂ along repulsive states that results in the production of very energetic nitrogen atoms.     

The history of titan,of Saturn's rings and magnetic field,and the nature of short-period comets

Titan in the past, just as Ganymede, had a massive ice envelope subjected to volumetric electrolysis under the action of unipolar electric current generated through the interaction of the satellite with Saturn's magnetosphere. The electrolysis products concentration required to cause explosion could become accumulated only under conditions of an exponential decay of Saturn's magnetic field in time (with τ_? ≈ 0.55 Gyr) which implies a relict nature of the field and agrees with the present ideas on the planet's structure. The explosion of the electrolysis products contained in the ice envelope resulted in Titan's having lost ～13% of its mass in the form of gas (mainly of water vapor) and solid ice fragments, as well as in the appearance on Titan of an atmosphere (of volatile products from incomplete combustion of hydrogen and hydrocarbons) and a deep (～1000 km) ocean of liquid water. The presence of liquid water on Titan's surface is confirmed by an analysis of the available microwave measurements of brightness temperature. The condensation of the water vapor lost by Titan produced the visible inner rings of Saturn while large solid fragments of the ice envelope govern their dynamics. These are also located in the gap between Rhea and Titan (the G ring?). Most of the ice fragments were swept out from Saturn's system through perturbations by Titan. They made up a reservoir of cometary nuclei beyond Jupiter's orbit. Arguments are presented in favor of a recent (3–10 thousand years ago) explosion of Titan. Some implications from these concepts, lending themselves to observational testing, are pointed out.     

The 6300 Å O1D airglow and dissociative recombination

Measurements of night-time 6300 Å airglow intensities at the Arecibo Observatory have been compared with dissociative recombination calculations based on electron densities derived from simultaneous incoherent backscatter measurements. The agreement indicates that the nightglow can be fully accounted for by dissociative recombination. Thecomparisons are examined to determine the importance of quenching, heavy ions, ionization above the F-layer peak, and the temperature parameter of the model atmosphere. Comparable fits between the observed and calculated intensities are found for several available model atmos- pheres (e.g. CIRA, Jacchia). The least-squares fitting process, used to make the comparisons, produces comparable fits over a wide range of combinations of neutral densities and of reaction constants. Yet, the fitting places constraints upon the possible combinations: these constraints indicate that the latest laboratory chemical constants and densities extrapolated to a base altitude are mutually consistent. However, by imposing an additional constraint, an aero- nomically derived preference is given for about one O(^1D) per combination. A preference is also given for the lower base densities of O₂ derived from rockets rather than from models. Altitude profiles for the 6300 Å and 5577 Å emissions are deduced. In the early evening, there are no large discrepancies in the fits that might indicate an effect from elicited states of O₊, vibrational excitation of O₂, or both. The technique of comparing observed and cal- culated 6300 Å intensities has considerable potential as an aeronomical tool for examination of other possible sources of emission and for determination of relative changes in the neutral atmosphere.     

Intensity variation of atomic oxygen red line in the day airglow with solar activity

Rates of production of O(¹ D) atoms in the upper atmosphere by photodissociation of O₂, dissociative recombination of O₂ ⁺, NO⁺ and electron impact excitation of O(³ P) have been calculated for low, medium and high levels of solar activity. Variations with solar activity, of neutral and ionic composition, electron and neutral temperatures of the upper atmosphere and solar extreme ultraviolet fluxes incident on it have been taken into consideration.Emission rates ofOi red line (6300Å) have been computed taking into account the deactivation both by molecular oxygen and nitrogen. It has been shown that the integrated intensity from low to high activity period varies by approximately an order of magnitude in agreement with the results of experimental observations.     

Near-surface winds at the Huygens site on Titan: Interpretation by means of a general circulation model

This study aims at interpreting the zonal and meridional wind in Titan's troposphere measured by the Huygens probe by means of a general circulation model. The numerical simulation elucidates the relative importance of the seasonal variation in the Hadley circulation and Saturn's gravitational tide in affecting the actual wind profile. The observed reversal of the zonal wind at two altitudes in the lower troposphere can be reproduced with this model only if the near-surface temperature profile is asymmetric about the equator and substantial seasonal redistribution of angular momentum by the variable Hadley circulation takes place. The meridional wind near the surface is mainly caused by the meridional pressure gradient and is thus a manifestation of the Hadley circulation. Southward meridional wind in the PBL (planetary boundary layer) is consistent with the near-surface temperature at the equator being lower than at mid southern latitudes. Even small changes in the radiative heating profile in the troposphere can substantially affect the mean zonal and meridional wind including their direction. Saturn's gravitational tide is rather weak at the Huygens site due to the proximity to the equator, and does not clearly manifest itself in the instantaneous vertical profile of wind. Nevertheless, the simulated descent trajectory is more consistent with the observation if the tide is present. Because of a different force balance in Titan's atmosphere from terrestrial conditions, PBL-specific wind systems like on Earth are unlikely to exist on Titan.