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.     

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.     

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.     

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.     

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.     

Detection of CH3D on Titan

We report the detection of ¹³CH₃D in Titan's stratosphere from Cassini/CIRS infrared spectra near 8.7 μm. Fitting simultaneously the ν₆ bands of both ¹³CH₃D and ¹²CH₃D and the ν₄ band of CH₄, we derive a D/H ratio equal to and a ¹²C/¹³C ratio in deuterated methane of , consistent with that measured in normal methane.     

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.     

Particle size and abundance of HC3N ice in Titan’s lower stratosphere at high northern latitudes

Up to now, there has been no corroboration from Cassini CIRS of the Voyager IRIS-discovery of cyanoacetylene (HC₃N) ice in Titan’s thermal infrared spectrum. We report the first compelling spectral evidence from CIRS for the ν₆ HC₃N ice feature at 506 cm⁻¹ at latitudes 62°N and 70°N, from which we derive particle sizes and column abundances in Titan’s lower stratosphere. We find mean particle radii of 3.0 μm and 2.3 μm for condensed HC₃N at 62°N and 70°N, respectively, and corresponding ice phase molecular column abundances in the range 1-10 × 10¹⁶ mol cm⁻². Only upper limits for cloud abundances can be established at latitudes of 85°N, 55°N, 30°N, 10°N, and 15°S. Under the assumption that cloud tops coincide with the uppermost levels at which HC₃N vapor saturates, we infer geometric thicknesses for the clouds equivalent to 10-20 km or so, with tops at 165 km and 150 km at 70°N and 62°N, respectively.     

Seasonal variation of Titan's stratospheric ethylene (C2H4) observed

All previous observations of seasonal change on Titan have been of physical phenomena such as clouds and haze. We present here the first observational evidence of chemical change in Titan's atmosphere. Images taken during 1999-2002 (late southern spring on Titan) with the W.M. Keck I 10-meter telescope at 8-13 μm show a significant accumulation of ethylene (C₂H₄) in the south polar stratosphere as well as north-south stratospheric temperature variation (colder at poles). Our observations restrict this newly discovered south polar ethylene accumulation to latitudes south of 60° S. The only other observations of the spatial distribution of C₂H₄ were those of Voyager I, which found a significant north polar accumulation in early northern spring. We see no build-up in the north, although the highest northern latitudes are obstructed from view in the current season. Our observations constrain any unobserved north polar accumulation of C₂H₄ to north of 50° N latitude. Comparison of the Voyager I results with our new results show seasonal chemical change has occurred in Titan's atmosphere.     

Laboratory kinetics of C2H radical reactions with ethane, propane, and n-butane at T = 96-296 K: implications for Titan

The kinetics of the reactions of C₂H radical with ethane (k₁), propane (k₂), and n-butane (k₃) are studied over the temperature range of T = 96-296 K with a pulsed Laval nozzle apparatus that utilizes a pulsed laser photolysis-chemiluminescence technique. The C₂H decay profiles in the presence of both the alkane reactant and O₂ are monitored by the CH(A²Δ) chemiluminescence tracer method. The results, together with available literature data, yield the following Arrhenius expressions: k₁(T) = (0.51 ± 0.06) × 10⁻¹⁰ exp[(−76 ± 30)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-800 K), k₂(T) = (0.98 ± 0.32) × 10⁻¹⁰exp[(−71 ± 60)K/T] cm³ molecule⁻¹ s⁻¹ (T = 96-361 K), and k₃(T) = (1.23 ± 0.26) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ (T = 96-297 K). At T = 296 K, k₁ is measured as a function of total pressure and has little or no pressure dependence. The results from this work support a direct hydrogen abstraction mechanism for the title reactions. Implications to the atmospheric chemistry of Titan are discussed.     

New Millimeter Heterodyne Observations of Titan: Vertical Distributions of Nitriles HCN, HC3N, CH3CN, and the Isotopic Ratio N/N in Its Atmosphere

High sensitivity observations were performed at 1.2- and 3-mm wavelengths with the IRAM 30-m telescope (Spain) between April 1996 and December 1999 to investigate the nitrile composition of Titan's stratosphere. A part of our dataset consists of high resolution spectra of HC¹⁴N taken at 88.6 GHz as well as spectra of HC¹⁵N recorded at 258.16 GHz. From a thorough analysis of both lines and with the help of appropriate radiative transfer calculations we show that the isotopic ratio ¹⁵N/¹⁴N is strongly enhanced compared to the terrestrial value. We propose that the range 3.9-4.5 should be considered as a basis for the enrichment factor. Five individual lines of HC₃N were measured at 39-kHz resolution using a frequency-switched technique. Several CH₃CN features were recorded at 78-kHz resolution in two transitions around 147.6 and 220.7 GHz. The high spectral resolution and the good signal-to-noise ratio affecting the spectra permit us to retrieve disk-averaged vertical profiles for HCN up to 450 km and for HC₃N and CH₃CN up to 500 km. Comparison of our inferred vertical profiles with relevant results of presently published photochemical models is presented. We show that the profiles of HCN and HC₃N predicted by various authors below 450-km altitude appear inconsistent with our new observations. We find that the three distributions present very different gradients of abundance below 200-km altitude down to the condensation levels around 80 km. In the upper stratosphere HC₃N and CH₃CN have approximately the same mixing ratio of about 4×10⁻⁸ at 450 km, at least one order of magnitude lower than that of HCN. In the same time, another nitrile HC₅N has been searched for by observing four transitions located between 109 and 221 GHz. As no spectral features could be detected after several hours of integration time, we propose an upper limit for the mixing ratio equal to 4×10⁻¹⁰ assuming a uniform distribution of this compound in the lower stratosphere.     

Impact-induced N2 production from ammonium sulfate: Implications for the origin and evolution of N2 in Titan’s atmosphere

Chemical reactions and volatile supply through hypervelocity impacts may have played a key role for the origin and evolution of both planetary and satellite atmospheres. In this study, we evaluate the role of impact-induced N₂ production from reduced nitrogen-bearing solids proposed to be contained in Titan’s crust, ammonium sulfate ((NH₄)₂SO₄), for the replenishment of N₂ to the atmosphere in Titan’s history. To investigate the conversion of (NH₄)₂SO₄ into N₂ by hypervelocity impacts, we measured gases released from (NH₄)₂SO₄ that was exposed to hypervelocity impacts created by a laser gun. The sensitivity and accuracy of the measurements were enhanced by using an isotope labeling technique for the target. We obtained the efficiency of N₂ production from (NH₄)₂SO₄ as a function of peak shock pressure ranging from ∼8 to ∼45 GPa. Our results indicate that the initial and complete shock pressures for N₂ degassing from (NH₄)₂SO₄ are ∼10 and ∼25 GPa, respectively. These results suggest that cometary impacts on Titan (i.e., impact velocity v_i > ∼8 km/s) produce N₂ efficiently; whereas satellitesimal impacts during the accretion (i.e., v_i < 4 km/s) produce N₂ only inefficiently. Even when using the proposed small amount of (NH₄)₂SO₄ content in the crust (∼4 wt.%) (Fortes, A.D. et al., 2007. Icarus 188, 139-153), the total amount of N₂ provided through cometary impacts over 4.5 Ga reaches ∼2-6 times the present atmospheric N₂ (i.e., ∼7 × 10²⁰-2 × 10²¹ [mol]) based on the measured production efficiency and results of a hydrodynamic simulation of cometary impacts onto Titan. This implies that cometary impacts onto Titan’s crust have the potential to account for a large part of the present N₂ through the atmospheric replenishment after the accretion.     

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.     

Sulfur chemistry in the Venus mesosphere from SO2 and SO microwave spectra

First measurements of SO₂ and SO in the Venus mesosphere (70-100 km) are reported. This altitude range is distinctly above the ∼60-70 km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO₂, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO₂ and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO₂ and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO₂/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO₂ and SO at 85-100 km than at 70-85 km. The observed increase of SO₂ mixing ratio with altitude requires that the primary SO₂ source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO₂. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO + SO₂) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO₂.     

Characterization of zonal winds in the stratosphere of Titan with UVES

Titan has been observed with UVES, the UV-Visual Echelle Spectrograph at the Very Large Telescope, with the aim of characterizing the zonal wind flow. We use a retrieval scheme originally developed for absolute stellar accelerometry [Connes, P., 1985. Astrophys. Space Sci., 110, 211-255] to extract the velocity signal by simultaneously taking into account all the lines present in the spectrum. The method allows to measure the Doppler shift induced at a given point by the zonal wind flow, with high precision. The short-wavelength channel (4200-5200 Å) probes one scale height higher than the long-wavelength one (5200-6200 Å), and we observe statistically significant evidence for stronger winds at higher altitudes. The results show a high dispersion. Globally, we detect prograde zonal winds, with lower limits of 62 and 50 m s⁻¹ at the regions centered at 200 and 170 km altitude, but approximately a quarter of the measurements indicates null or retrograde winds.     

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

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

Impact of the seasonal variations of composition on the temperature field of Titan’s stratosphere

We investigate the role of seasonal variations of Titan’s stratospheric composition on the temperature. We use a general circulation model coupled with idealized chemical tracers that reproduce variations of ethane (C₂H₆), acetylene (C₂H₂), and hydrogen cyanide (HCN). Enhancement of the mole fractions of these compounds, at high latitudes in the winter hemisphere relative to their equatorial values, induces a relative decrease in temperature above approximately 0.2 mbar, with a peak amplitude around −20 K, and a relative increase in temperature below, around 1 mbar, with a peak amplitude around +7 K. These thermal effects are mainly due to the variations of the cooling to space induced by the varying distributions. The ethane, acetylene, and hydrogen cyanide variations affect the cooling rates in a similar way, with the dominant effect being due to ethane, though its latitudinal variations are small.     

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.     

Detection of C2HD and the D/H ratio on Titan

We report here the first detection of mono-deuterated acetylene (acetylene-d1, C₂HD) in Titan's atmosphere from the presence of two of its emission bands at 678 and 519 cm⁻¹ as observed in CIRS spectral averages of nadir and limb observations taken between July 2004 and mid-2007. By using new laboratory spectra for this molecule, we were able to derive its abundance at different locations over Titan's disk. We find the C₂HD value () to be roughly constant with latitude from the South to about 45° N and then to increase slightly in the North, as is the case for C₂H₂. Fitting the 678 cm⁻¹ν₅ band simultaneously with the nearby C₂H₂ 729 cm⁻¹ν₅ band, allows us to infer a D/H ratio in acetylene on Titan with an average of the modal values of 2.09±0.45×¹⁰⁻⁴ from the nadir observations, the uncertainties being mainly due to the vertical profile used for the fit of the acetylene band. Although still subject to significant uncertainty, this D/H ratio appears to be significantly larger than the one derived in methane from the CH₃D band (upper limit of 1.5×¹⁰⁻⁴; Bézard, B., Nixon, C.A., Kleiner, I., Jennings, D.E., 2007. Icarus, 191, 397-400; Coustenis, A., Achterberg, R., Conrath, B., Jennings, D., Marten, A., Gautier, D., Bjoraker, G., Nixon, C., Romani, P., Carlson, R., Flasar, M., Samuelson, R.E., Teanby, N., Irwin, P., Bézard, B., Orton, G., Kunde, V., Abbas, M., Courtin, R., Fouchet, Th., Hubert, A., Lellouch, E., Mondellini, J., Taylor, F.W., Vinatier, S., 2007. Icarus 189, 35-62). From the analysis of limb data we infer D/H values of (at 54° S), (at 15° S), (at 54° N) and (at 80° N), which average to a mean value of 1.63±0.27×¹⁰⁻⁴.     

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.