Chemical sources of haze formation in Titan's atmosphere

A prominent feature of Titan's atmosphere is a thick haze region that acts as the end product of hydrocarbon and nitrile chemistry. Using a one-dimensional photochemical model, an investigation into the chemical mechanisms responsible for the formation of this haze region is conducted. The model derives profiles for Titan's atmospheric constituents that are consistent with observations. Included is an updated benzene profile that matches more closely with—recent ISO observations (Icarus 161 (2003) 383), replacing the profile given in the benzene study of Wilson et al. (J. Geophys. Res. 108 (2003) 5014). Using these profiles, pathways from polyynes, aromatics, and nitriles are considered, as well as possible copolymerization among the pathways. The model demonstrates that the growth of polycyclic aromatic hydrocarbons throughout the lower stratosphere plays an important role in furnishing the main haze layer, with nitriles playing a secondary role. The peak chemical production of haze layer ranges from 140 to 300 km peaking at an altitude of 220 km, with a production rate of 3.2×10⁻¹⁴ gcm⁻² s⁻¹. Possible mechanisms for polymerization and copolymerization and suggestions for further kinetic study are discussed, along with the implications for the distribution of haze in Titan's atmosphere.     

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

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

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

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

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.     

Global and temporal variations in hydrocarbons and nitriles in Titan's stratosphere for northern winter observed by Cassini/CIRS

Mid-infrared spectra measured by Cassini's Composite InfraRed Spectrometer (CIRS) between July 2004 and January 2007 (Ls=293°-328°) have been used to determine stratospheric temperature and abundances of C₂H₂, C₃H₄, C₄H₂, HCN, and HC₃N. Over 65,000 nadir spectra with spectral resolutions of 0.5 and 2.5 cm⁻¹ were used to probe spatial and temporal composition variations in Titan's stratosphere. Cassini's 180° orbital transfer in mid-2006 allowed low emission angle observations of the north polar region for the first time in the mission and allowed us to probe the full latitude range. We present the first measurements of composition variations within the polar vortex, which display increasing abundances right up to 90° N. The lack of a homogeneous abundance-latitude variation within the vortex indicates limited horizontal mixing and suggests that subsidence is greatest at the vortex core. Contrary to numerical model predictions and tropospheric cloud observations, we do not see any evidence for a secondary circulation cell near the south pole, which suggests a single Hadley-type circulation in the stratosphere at this epoch. This difference can be reconciled if the secondary cell is restricted to altitudes below 100 km, where there is no sensitivity in our data. Temporal variations in composition were observed in the south, with volatile species becoming less abundant as the season progressed. The observed variations are compared to numerical model predictions and observations from Voyager.     

Methane, ethane, and mixed clouds in Titan's atmosphere: Properties derived from microphysical modeling

Theoretical arguments point to and recent observations confirm the existence of clouds in Titan's atmosphere, yet we possess very little data on their particle size, composition and formation mechanism. A time-dependent microphysical model is used to study the evolution of ice clouds in Titan's atmosphere. The model simulates nucleation, condensational growth, evaporation, coagulation, and transport of particles in a column of atmosphere. A variety of cloud compositions are studied, including pure ethane clouds, pure methane clouds, and mixed methane-ethane clouds (all with tholin cores). The abundance of methane cloud particles may be limited by the number of ethane coated tholin nuclei rather than the number of tholins with hydrocarbon coatings. However, even the condensation of methane onto these relatively sparse ethane/tholin cloud particles is sufficient to keep the methane close to saturation. Typical methane supersaturations are of order 0.06 on the average. For simulations which take into account recent lab measurements indicating it is relatively easy for methane to nucleate onto tholin particles without an ethane-layer present, the three types of clouds (methane, ethane, and mixed) exist simultaneously. Pure methane clouds are the most abundant cloud type and serve to lower the supersaturation to about 0.04. Cloud production does not require a continuous surface source of methane. However, clouds produced by mean motions are not the visible methane clouds seen in recent Cassini and ground-based observations. Ethane clouds in the troposphere almost instantaneously nucleate methane to form mixed clouds. However, a thin ethane ‘haze’ remains just above the tropopause for some scenarios and the mixed clouds at the tropopause remain ?50% ethane by mass. Also, evaporation of methane from the mixed cloud particles near the surface leaves a thicker layer of ethane cloud particles at ∼10 km. Nevertheless, the precipitation rate of methane to Titan's surface is between 0.001 and 0.5 cm/terrestrial-year, depending on various initial conditions such as critical saturation, size and abundance of cloud condensation nuclei, surface sources and eddy diffusion.     

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

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

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

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

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

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

Condensed species in Titan's atmosphere: Identification of crystalline propionitrile (C2H5CN, CH3CH2CN) based on laboratory infrared data

We report the results of infrared studies of crystalline C₂H₅CN at several temperatures between 15 and 160 K. A case is made for the identification of crystalline C₂H₅CN in the stratosphere from the Voyager IRIS spectrum of Titan.     

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.     

Vertical abundance profiles of hydrocarbons in Titan's atmosphere at 15° S and 80° N retrieved from Cassini/CIRS spectra

Limb spectra recorded by the Composite InfraRed Spectrometer (CIRS) on Cassini provide information on abundance vertical profiles of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₃H₈, C₄H₂, C₆H₆ and HCN, along with the temperature profiles in Titan's atmosphere. We analyzed two sets of spectra, one at 15° S (Tb flyby) and the other one at 80° N (T3 flyby). The spectral range 600-1400 cm⁻¹, recorded at a resolution of 0.5 cm⁻¹, was used to determine molecular abundances and temperatures in the stratosphere in the altitude range 100-460 km for Tb and 170-495 km for T3. Both temperature profiles show a well defined stratopause, at around 310 km (0.07 mbar) and 183 K at 13° S, and 380 km (0.01 mbar) with 207 K at 80° N. Near the north pole, stratospheric temperatures are colder and mesospheric temperatures are warmer than near the equator. C₂H₂, C₂H₆, C₃H₈ and HCN display vertical mixing ratio profiles that increase with height at 15° S and 80° N, consistent with their formation in the upper atmosphere, diffusion downwards and condensation in the lower stratosphere, as expected from photochemical models. The CH₃C₂H and C₄H₂ mixing ratios also increase with height at 15° S. But near the north pole, their profiles present an unexpected minimum around 300 km, observed for the first time thanks to the high vertical resolution of the CIRS limb data. C₂H₄ is the only molecule having a vertical abundance profile that decreases with height at 15° S. At 80° N, it also displays a minimum of its mixing ratio around the 0.1-mbar level. For C₆H₆, an upper limit of 1.1 ppb (in the 0.3-10 mbar range) is derived at 15° S, whereas a constant mixing ratio profile of is inferred near the north pole. At 15° S, the vertical profile of HCN exhibits a steeper gradient than other molecules, which suggests that a sink for this molecule exists in the stratosphere, possibly due to haze formation. All molecules display a more or less pronounced enrichment towards the north pole, probably due, in part, to subsidence of air at the north (winter) pole that brings air enriched in photochemical compounds from the upper atmosphere to lower levels.     

IR band intensities of DC3N and HC3N: Implication for observations of Titan's atmosphere

We have obtained the infrared spectra and the corresponding absolute band intensities for two HC₃N isotopomers: DC₃N and HC₃¹⁵N. Our results for DC₃N are in good agreement with previous measurements except for the ν₂ and ν₃ stretching modes. For HC₃¹⁵N, this study is the first including intensity measurements.We have also studied the possible detection of these isotopomers in Titan's atmosphere using the CIRS spectrograph onboard the Cassini spacecraft. Our simulation of the expected spectra shows that for a signal-to-noise ratio better than 100, the ¹⁵N isotopomer of HC₃N could be detected. But, further study of HC₃N hot bands are needed since some of them overlap the HC₃¹⁵N Q-branch.     

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

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

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.     

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.     

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.