Radial distribution of production rates, loss rates and densities corresponding to ion masses ?40 amu in the inner coma of Comet Halley: Composition and chemistry

In this paper we have studied the chemistry of C, H, N, O, and S compounds corresponding to ions of masses ?40 amu in the inner coma of the Comet 1P/Halley. The production rates, loss rates, and ion mass densities are calculated using the Analytical Yield Spectrum approach and solving coupled continuity equation controlled by the steady state photochemical equilibrium condition. The primary ionization sources in the model are solar EUV photons, photoelectrons, and auroral electrons of the solar wind origin. The chemical model couples ion-neutral, electron-neutral, photon-neutral and electron-ion reactions among ions, neutrals, electrons, and photons through over 600 chemical reactions. Of the 46 ions considered in the model the chemistry of 24 important ions (viz., CH₃OH⁺₂, H₃CO⁺, NH⁺₄, H₃S⁺, H₂CN⁺, H₂O⁺, NH⁺₃, CO⁺, C₃H⁺₃, OH⁺, H₃O⁺, CH₃OH⁺, C₃H⁺₄, C₂H⁺₂, C₂H⁺, HCO⁺, S⁺, CH⁺₃, H₂S⁺, O⁺, C⁺, CH⁺₄, C⁺₂, and O⁺₂) are discussed in this paper. At radial distances <1000 km, the electron density is mainly controlled by 6 ions, viz., NH⁺₄, H₃O⁺, CH₃OH⁺₂, H₃S⁺, H₂CN⁺, and H₂O⁺, in the decreasing order of their relative contribution. However, at distances >1000 km, the 6 major ions are H₃O⁺, CH₃OH⁺₂, H₂O⁺, H₃CO⁺, C₂H⁺₂, and NH⁺₄; along with ions CO⁺, OH⁺, and HCO⁺, whose importance increases with further increase in the radial distance. It is found that at radial distances greater than ∼1000 km (±500 km) the major chemical processes that govern the production and loss of several of the important ions in the inner coma are different from those that dominate at distances below this value. The importance of photoelectron impact ionization, and the relative contributions of solar EUV, and auroral and photoelectron ionization sources in the inner coma are clearly revealed by the present study. The calculated ion mass densities are compared with the Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500, 3500, and 6000 km. There is a reasonable agreement between the model calculation and the Giotto measurements. The nine major peaks in the IMS spectra between masses 10 and 40 amu are reproduced fairly well by the model within a factor of two inside the ionopause. We have presented simple formulae for calculating densities of the nine major ions, which contribute to the nine major peaks in the IMS spectra, throughout the inner coma that will be useful in estimating their densities without running the complex chemical models.     

The lower ionosphere of Titan

Ionization of the atmosphere of Titan by galactic cosmic rays is a very significant process throughout the altitude range of 100 to 400 km. An approximate form of the Boltzmann equation for cosmic ray transport has been used to obtain local ionization rates. Models of both ion and neutral chemistry have been employed to compute electron and ion density profiles for three different values of the H₂/CH₄ abundance ratio. The peak electron density is of the order 10³ cm^?3. The most abundant positive ions are C₂H₉⁺ and C₃H₉⁺, while the predicted densities of the negative ions H^? and CH₃^? are very small (<10^?4 that of the positive ions). It is suggested that inclusion of the ion chemistry is important in the computation of the H and CH₃ density profiles in the lower ionosphere.     

Temporally varying ethylene emission on Jupiter

Ethylene (C₂H₄) emission has been measured in the poles and equator of Jupiter. The 949 cm⁻¹ spectra were recorded with a high resolution spectrometer at the McMath-Pierce telescope at Kitt Peak in October-November 1998 and at the Infrared Telescope Facility at Mauna Kea in June 2000. C₂H₄ is an important product of methane chemistry in the outer planets. Knowledge of its abundance can help discriminate among the various proposed sets of CH₄ photolysis branching ratios at Ly-α, and determine the relative importance of the reaction pathways that produce C₂H₂ and C₂H₆. In the equatorial region the C₂H₄ emission is weak, and we were only able to detect it at high air-mass, near the limb. We derive a peak equatorial molar abundance of C₂H₄ of 4.5×¹⁰⁻⁷-1.7×¹⁰⁻⁶ near 2.2×¹⁰⁻³ mbar, with a total column of 5.7×¹⁰¹⁴-2.2×¹⁰¹⁵ molecules cm⁻² above 10 mbar depending upon choice of thermal profile. We observed enhanced C₂H₄ emission from the poles in the regions where auroras are seen in X-ray, UV, and near infrared images. In 2000 we measured a short-term change in the distribution of polar C₂H₄ emission; the emission in the north IR auroral “hot spot” decreased by a factor of three over a two-day interval. This transient behavior and the sensitivity of C₂H₄ emission to temperature changes near its contribution peak at 5-10 microbar suggests that the polar enhancement is primarily a thermal effect coupled with vertical transport. Comparing our observations from Kitt Peak and Mauna Kea shows that the C₂H₄ emission of the northern non-“hot spot” auroral regions did not change over the three-year period while that in the southern polar regions decreased.     

A photochemical model of Titan's atmosphere and ionosphere

A global-mean model of coupled neutral and ion chemistry on Titan has been developed. Unlike the previous coupled models, the model involves ambipolar diffusion and escape of ions, hydrodynamic escape of light species, and calculates the H₂ and CO densities near the surface that were assigned in some previous models. We tried to reduce the numbers of species and reactions in the model and remove all species and reactions that weakly affect the observed species. Hydrocarbon chemistry is extended to C₁₂H₁₀ for neutrals and C₁₀H⁺₁₁ for ions but does not include PAHs. The model involves 415 reactions of 83 neutrals and 33 ions, effects of magnetospheric electrons, protons, and cosmic rays. UV absorption by Titan's haze was calculated using the Huygens observations and a code for the aggregate particles. Hydrocarbon, nitrile, and ion chemistries are strongly coupled on Titan, and attempt to calculate them separately (e.g., in models of ionospheric composition) may result in significant error. The model densities of various species are typically in good agreement with the observations except vertical profiles in the stratosphere that are steeper than the CIRS limb data. (A model with eddy diffusion that facilitates fitting to the CIRS limb data is considered as well.) The CO densities are supported by the O⁺ flux from Saturn's magnetosphere. The ionosphere includes a peak at 80 km formed by the cosmic rays, steplike layers at 500-700 and 700-900 km and a peak at 1060 km (SZA = 60°). Nighttime densities of major ions agree with the INMS data. Ion chemistry dominates in the production of bicyclic aromatic hydrocarbons above 600 km. The model estimates of heavy positive and negative ions are in reasonable agreement with the Cassini results. The major haze production is in the reactions C₆H + C₄H₂, C₃N + C₄H₂, and condensation of hydrocarbons below 100 km. Overall, precipitation rate of the photochemical products is equal to 4-7 kg cm⁻² Byr⁻¹ (50-90 m Byr⁻¹ while the global-mean depth of the organic sediments is ∼3 m). Escape rates of methane and hydrogen are 2.9 and 1.4 kg cm⁻² Byr⁻¹, respectively. The model does not support the low C/N ratio observed by the Huygens ACP in Titan's haze.     

An experimental study of the reaction kinetics of C2(XΣg) with hydrocarbons (CH4, C2H2, C2H4, C2H6 and C3H8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.     

Jupiter's hydrocarbon polar brightening: Discovery of 3-micron line emission from south polar CH4, C2H2, and C2H6

Jupiter exhibits bright H⁺₃ auroral arcs at 3-4 microns that cool the hot (>1000 K) ionosphere above the ∼¹⁰−7 bar level through the infrared bands of this trace constituent. Below the ¹⁰−7 bar level significant cooling proceeds through infrared active bands of CH₄, C₂H₂, and C₂H₆. We report the discovery of 3-micron line emission from these hydrocarbon species in spectra of the jovian south polar region obtained on April 18 and 20, 2006 (UT) with CGS4 on the United Kingdom Infrared Telescope. Estimated cooling rates through these molecules are 7.5×¹⁰−3, 1.4×¹⁰−3, and , respectively, for a total nearly half that of H⁺₃. We derive a temperature of 450 ± 50 K in the ¹⁰−7-¹⁰−5 bar region from the C₂H₂ lines.     

A determination of the composition of the Saturnian stratosphere using the IUE

We reduced ultraviolet spectra of Saturn from the IUE satellite to produce a geometric albedo of the planet from 1500 to 3000 Å. By matching computer models to the albedo we determined a chemical composition consistent with the data. This model includes C₂H₂ and C₂H₆ with mixing ratios and distributions of (9 ± 3) × 10^?8 in the top 20 mbar of the atmosphere with none below for C₂H₂ and (6 ± 1) × 10^?6 also in the top 20 mbar with none below for C₂H₆. The C₂H₂ and C₂H₆ distributions and the C₂H₆ mixing ratio are taken directly from the Voyager IRIS model [R. Courtin et al., Bull. Amer. Astron. Soc.13, 722 (1981), and private communication]. The Voyager IRIS model also includes PH₃, which is not consistent with the uv albedo from 1800 to 2400 Å. Our model requires a previously unidentified absorber to explain the albedo near 1600 Å. After considering several candidates, we find that the best fit to the data is obtained with H₂O, having a column density of (6 ± 1) × 10^?3 cm-am.     

Mixing ratios of methane,ethane, and acetylene in Neptune's stratosphere

Matching computed spectra for the ν₄ band of methane, the ν₉ band of ethane, and the R branch of the ν₅ band of acetylene to observed spectra for Neptune suggests mixing ratios of CH₄/H₂ ～ 10^?3?10^?2, C₂H₆/H₂ ～ 10^?6, and C₂H₂/H₂ ～ 10^?8 in the stratosphere.     

Spectra Of Split Comet C/1999 S4 (Linear)

We obtained spectra of comet C/1999 S4 (LINEAR) with the UAGS spectrograph(long slit and CCD) installed on the 1-m Zeiss reflector of the SAO of the RAS(Northern Caucuses, Nizhny Arkhyz) on July 23/24, 26/27 and 27/28, 2000. OnJuly 22/23, before the splitting of the cometary nucleus, several emission lines,such as C₂, C₃, CN, NH, CH, NH₂, CO⁺, H₂O⁺ wereclearly identified in the spectra. The inspections of the CCD spectra obtainedon July 27/28, 2000 reveals only very weak emission lines superimposed on thesolar reflection spectrum. From analyzing the surface brightness profile of C₂ along the slit the velocity of separation of two secondary fragments (V = 10 km/h) and the energy of the fragment separation (E = 8.7 × 10¹⁵ erg) were estimated. A luminescence cometary continuum of 26% of the total continuum level is detected in the spectra of the comet at 5000 Å. Possible mechanisms of nucleus splitting are discussed.     

Models of the cometary coma in which abundances are calculated for various heliocentric distances

One-dimensional radial models of the chemistry in cometary comae have been constructed for heliocentric distances ranging from 2 to 0.125 AU. The coma's opacity to solar radiation is included and photolytic reaction rates are calculated. A parent volatile mixture similar to that found in interstellar molecular clouds is assumed. Profiles through the coma of number density and column density are presented for H₂O, OH, O, CN, C₂, C₃, CH, and NH₂. Whole-coma abundances are presented for NH₂, CH, C₂, C₃, CN, OH, CO⁺, H₂O⁺, CH⁺, N₂⁺, and CO₂⁺.     

Meridional variations of C2H2 and C2H6 in Jupiter's atmosphere from Cassini CIRS infrared spectra

Hydrocarbons such as acetylene (C₂H₂) and ethane (C₂H₆) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10 to 1400 cm⁻¹ (1000-7 μm). In this paper we analyze a zonally averaged set of CIRS spectra taken at the highest (0.48 cm⁻¹) resolution, firstly to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the ν₄ band of CH₄, and in the troposphere at 150-400 mbar, via the H₂ absorption at 600-800 cm⁻¹. Stratospheric temperatures at 5 mbar are generally warmer in the north than the south by 7-8 K, while tropospheric temperatures show no such asymmetry. Both latitudinal temperature profiles however do show a pattern of maxima and minima which are largely anti-correlated between the two levels. We then use the derived temperature profiles to infer the vertical abundances of C₂H₂ and C₂H₆ by modeling tropospheric absorption (∼200 mbar) and stratospheric emission (∼5 mbar) in the C₂H₂ν₅ and C₂H₆ν₉ bands, and also emission of the acetylene (ν₄+ν₅)−ν₄ hotband (∼0.1 mbar). Acetylene shows a distinct north-south asymmetry in the stratosphere, with 5 mbar abundances greatest close to 20° N and decreasing from there towards both poles by a factor of ∼4. At 200 mbar in contrast, acetylene is nearly flat at a level of ∼3×¹⁰⁻⁹. Additionally, the abundance gradient of C₂H₂ between 10 and 0.1 mbar is derived, based on interpolated temperatures at 0.1 mbar, and is found to be positive and uniform with latitude to within errors. Ethane at both 5 and 200 mbar shows increasing VMR towards polar regions of ∼1.75 towards 70° N and ∼2.0 towards 70° S. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C₂H₂ and C₂H₆ by factors of 2.7 and 3.5, respectively, at latitude 70°. However, the lifetime of C₂H₆ in the stratosphere (3×¹⁰¹⁰ s at 5 mbar) is much longer than the dynamical timescale for meridional mixing inferred from Comet SL-9 debris (5-50×¹⁰⁸ s), and therefore the rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C₂H₂, the opposite occurs, with the relatively short photochemical lifetime (3×¹⁰⁷ s), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.     

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.     

Reflectance and transmittance spectra (2.2-2.4 μm) of ion irradiated frozen methanol

We present near-IR (2.2-2.4 μm) reflectance and transmittance spectra of frozen (16 and 77 K) methanol (CH₃OH) and water-methanol (1:1) mixtures before and after irradiation with 30 keV He⁺ and 200 keV H⁺ ions. Spectra of other simple hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆) and CO have also been obtained both to help in the identification of the new molecules formed after ion irradiation of methanol-rich ices, and to get insight into the question of the presence of simple frozen hydrocarbons on the surface of some objects in the outer Solar System. The results confirm what obtained by studies performed in different spectral ranges, namely the ion-induced formation of CO and CH₄, and, for the first time, evidence a strong decrease of the intensity of the methanol band at about 2.34 μm in comparison with that at 2.27 μm. The results are discussed in view of their relevance for icy objects in the Solar System (namely comets, Centaurs, and Kuiper belt objects) where CH₃OH has been observed or suggested to be present.     

Meridional distribution of CH3C2H and C4H2 in Saturn’s stratosphere from CIRS/Cassini limb and nadir observations

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C₄H₂) and methylacetylene (CH₃C₂H) mixing ratios in Saturn’s stratosphere, from 5 hPa up to 0.05 hPa and 80°S to 45°N. We find that the C₄H₂ and CH₃C₂H meridional distributions mimic that of acetylene (C₂H₂), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules.Poleward of 60°S, at 0.1 and 0.05 hPa, we find that the CH₃C₂H and C₄H₂ abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH₃C₂H and C₄H₂ production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes.Our derived mean mixing ratios at 0.5 hPa of (2.4 ± 0.3) × 10⁻¹⁰ for C₄H₂ and of (1.1 ± 0.3) × 10⁻⁹ for CH₃C₂H are compatible with the analysis of global-average ISO observations performed by Moses et al. (Moses, J.I., Bézard, B., Lellouch, E., Gladstone, G.R., Feuchtgruber, H., Allen, M. [2000a]. Icarus 143, 244-298). Finally, we provide values for the ratios [CH₃C₂H]/[C₂H₂] and [C₄H₂]/[C₂H₂] that can constrain the coupled chemistry of these hydrocarbons.     

A seasonal climate model of the atmospheres of the giant planets at the voyager encounter time: I. Saturn's stratosphere

A radiative seasonal model which incorporates a multilayer radiative transfer treatment at wave-lengths longward of 7 μm is presented and applied to Saturn's stratosphere. Opacities due to H₂-He, CH₄, C₂H₂, and C₂H₆ are included. Season-dependent insolation is shown to produce a strong hemispheric asymmetry decreasing with depth at the Voyager encounter times, and seasonal amplitudes of 30°K at the poles are predicted in the high stratosphere. The ring-modulated dependence of the insolation and the orbital eccentricity are shown to have a significant effect. Calculations agree closely with the Voyager 1 and 2 radio occultation ingress profiles recorded at 76°S and 36.5°S for CH₄/H₂ = 3.5 + 1.4/? 1.0 × 10^?3;the estimated errors include modeling systematic errors and uncertainties in the occultations profiles. The possible role of aerosols in the stratospheric heating is analyzed. The Voyager 2 egress profile recorded at 31°S cannot be reproduced by calculations. Some constraints on the C₂H₂ and C₂H₆ abundances are derived. The upper portion of the occultation profiles (p < 3mbar) can be matched for C₂H₂/H₂ = 1.0 + 1.3/?0.6 × 10^?7, C₂H₆/H₂ = 1.5 + 1.8/?0.9 × 10^?6 at 76°S and C₂H₂/H₂ = 4 + 6/?4 × 10^?8, C₂H₆/H₂ = 6 + 9/?6 × 10^?7 at 36.5°N. At the northern occultation latitude, the discrepancy with the concentrations derived from analysis of IRIS spectra by R. Courtin, D. Gautier, A. Marten, B. Bézard, and R. Hanel (1984, Astrophys. J.287) can be explained by a sharp variation of the mixing ratios of these gases with altitude in the upper stratosphere. Other interpretations are discussed.     

Cosmic ray synthesis of organic molecules in Titan's atmosphere

We have studied the possible synthesis of organic molecules by the absorption of galactic cosmic rays in an N₂CH₄H₂ Titan model atmosphere. The cosmic-ray-induced ionization results in peak electron densities of 2 × 10³ cm^?3, with NH₄⁺, C₃H₉⁺, and C₄H₉⁺ being among the important positive ions. Details of the ion and neutral chemistry relevant to the production of organic molecules are discussed. The potential importance of $\text{N}\text{(}{}^2\text{D)}$ reactions with CH₄ and H₂ is also demonstrated. Although the integrated production rate of organic matter due to the absorption of the cosmic ray cascade is much less than that by solar ultraviolet radiation, the production of nitrogen-bearing organic molecules by cosmic rays may be greater.     

Identification of C4H5, C4H4, C3H3 and CH3 radicals produced from the reaction of atomic carbon with propene: Implications for the atmospheres of Titan and giant planets and for the interstellar medium

We observed the products C₄H₅, C₄H₄, C₃H₃ and CH₃ of the C(³P) + C₃H₆ reaction using product time-of-flight spectroscopy and selective photoionization. The identified species arise from the product channels C₄H₅ + H, C₄H₄ + 2H and C₃H₃ + CH₃. Product isomers were identified via measurements of photoionization spectra and calculations of adiabatic ionization energy. Product C₄H₅ probably involves three isomers HCCCHCH₃, H₂CCCCH₃ and H₂CCCHCH₂. In contrast, products C₄H₄ and C₃H₃ involve exclusively HCCCHCH₂ and H₂CCCH, respectively. Reaction mechanisms are unraveled with crossed-beam experiments and quantum-chemical calculations. The ³P carbon atom attacks the π orbital of propene (C₃H₆) to form a cyclic complex c-H₂C(C)CHCH₃ that rapidly opens the ring to form H₂CCCHCH₃ followed by decomposition to HCCCHCH₃/H₂CCCCH₃/H₂CCCHCH₂ + H and H₂CCCH + CH₃; the corresponding branching ratios are 7:5:10:78 predicted with RRKM calculations at collision energy 4 kcal mol^?1. Nascent C₄H₅ with enough internal energy further decomposes to HCCCHCH₂ + H. Ratios of products C₄H₅, C₄H₄ and C₃H₃ are experimentally evaluated to be 17:8:75. This work provides a comprehensive look at product channels of the title reaction and gives implications for the formation of hydrocarbons in extra-terrestrial environments such as Titan and carbon-rich interstellar media. We suggest that the title reaction, hitherto excluded in any chemical networks, needs to be taken into account at least in the atmosphere of Titan and carbon-rich molecular clouds where rapid neutral–neutral reactions are dominant and carbon atoms and propene are abundant.     

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.     

Detection of new hydrocarbons in Uranus' atmosphere by infrared spectroscopy

Ethane (C₂H₆), methylacetylene (CH₃C₂H or C₃H₄) and diacetylene (C₄H₂) have been discovered in Spitzer 10-20 μm spectra of Uranus, with 0.1-mbar volume mixing ratios of (1.0±0.1)×¹⁰⁻⁸, (2.5±0.3)×¹⁰⁻¹⁰, and (1.6±0.2)×¹⁰⁻¹⁰, respectively. These hydrocarbons complement previously detected methane (CH₄) and acetylene (C₂H₂). Carbon dioxide (CO₂) was also detected at the 7-σ level with a 0.1-mbar volume mixing ratio of (4±0.5)×¹⁰⁻¹¹. Although the reactions producing hydrocarbons in the atmospheres of giant planets start from radicals, the methyl radical (CH₃) was not found in the spectra, implying much lower abundances than in the atmospheres of Saturn or Neptune where it has been detected. This finding underlines the fact that Uranus' atmosphere occupies a special position among the giant planets, and our results shed light on the chemical reactions happening in the absence of a substantial internal energy source.