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.     

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.     

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.     

Saturn's latitudinal C2H2 and C2H6 abundance profiles from Cassini/CIRS and ground-based observations

Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C₂H₂ and C₂H₆ emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm⁻¹ resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C₂H₂ and C₂H₆ across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C₂H₂ abundance at the 1.2 mbar level is (1.6±0.19)×¹⁰−7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C₂H₂ abundance jumps to (1.8±0.3)×¹⁰−7, approximately the equatorial value. The C₂H₆ abundance near the equator at the 2 mbar level is (0.7±0.1)×¹⁰−5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4±0.4)×¹⁰−5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the southern pole.     

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.     

Titan's aerosols: Comparison between our model and DISR findings

Our model [Dimitrov, V., Bar-Nun, A., 1999. A model of energy dependent agglomeration of hydrocarbon aerosol particles and implication to Titan's aerosol. J. Aerosol. Sci. 30(1), 35-49] describes the experimentally found polymerization of C₂H₂ and HCN to form aerosol embryos, their growth and adherence to form various aerosols objects [Bar-Nun, A., Kleinfeld, I., Ganor, E., 1988. Shape and optical properties of aerosols formed by photolysis of C₂H₂, C₂H₄ and HCN. J. Geophys. Res. 93, 8383-8387]. These loose fractal objects describe well the findings of DISR on the Huygens probe [Tomasko, M.G., Bézard, B., Doose, L., Engel, S., Karkoschka, E., 2008. Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere. Planet. Space Sci., this issue, doi:10.1016/j.pss.2007]. These include (1) various regular objects of R=(0.035-0.064)×10⁻⁶ m, as compared with DISR's 0.05×10⁻⁶ m; (2) diverse low and high fractal structures composed of random combinations of various regular and irregular objects; (3) the number density of fractal particles is 6.9×10⁶ m⁻³ at Z=100 km, as compared with DISR's finding of 5.0×10⁶ m⁻³ at Z=80 km; (4) the number of structural units per higher fractals in the atmosphere at Z∼100 km is (2400-2700), as compared with DISR's 3000, and their size being of R=(5.4-6.4)×10⁻⁶ m will satisfy this value and (5) condensation of CH₄ on the highly fractal structures could begin at the altitude where thin methane clouds were observed, filling somewhat the new open fractal structures.     

First Spitzer observations of Neptune: Detection of new hydrocarbons

We present the first spectra of Neptune taken with the Spitzer Space Telescope, highlighting the high-sensitivity, moderate-resolution 10-20 μm (500-1000 cm⁻¹) spectra. We report the discovery of methylacetylene (CH₃C₂H) and diacetylene (C₄H₂) with derived 0.1-mbar volume mixing ratios of (1.2±0.1)×¹⁰⁻¹⁰ and (3±1)×¹⁰⁻¹² respectively.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

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 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.     

Latitudinal variation of Saturn photochemistry deduced from spatially-resolved ultraviolet spectra

We obtained spatially-resolved ultraviolet spectra of Saturn in 1994 with the Faint Object Spectrometer and Goddard High Resolution Spectrograph of the Hubble Space Telescope. We observed four areas on the planet at 15° N, 33° S, 41° S, and 52° S, with a field-of-view of less than 2 × 2 arcsec², compared to the 16-arcsec planet diameter. The wavelength range, 1550-2300 Å, encompasses absorption from major hydrocarbons (C₂H₆, C₂H₄, C₂H₂, CH₃C₂H, C₄H₂) and water. We find global hydrocarbon abundances and a C₂H₂ vertical distribution compatible with infrared observations, in contrast with previous analyses of ultraviolet spectra. The stratospheric haze opacity decreases from polar region to the equator. Saturn mid-latitudes are photochemically distinct from the rest of the planet. At 33° S, the spectrum requires either (1) a distinctly different C₂H₂ vertical distribution or (2) a locally enhanced water abundance. At 41° S, the hydrocarbon abundance exhibits a local minimum, within a global trend of increasing abundance from equator to pole. This global trend may result from an increased abundance of short-lived hydrocarbons such as C₄H₂. Photochemical models predict a depletion of hydrocarbon molecules in the presence of stratospheric water [Moses et al., 2000. Icarus 143, 166-202]. These results are consistent with a localized influx of water, in the form of high charge to mass ratio particles, flowing into Saturn's atmosphere at latitudes magnetically linked to the rings.     

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.     

Flowing afterglow studies of temperature dependencies for electron dissociative recombination of HCNH, CH3CNH and CH3CH2CNH and their symmetrical proton-bound dimers

A study has been made using a variable temperature flowing afterglow Langmuir probe technique (VT-FALP) to determine the equilibrium temperature dependencies of the dissociative electron-ion recombination of the protonated cyanide ions (RCNH⁺, where R=H, CH₃ and C₂H₅) and their symmetrical proton-bound dimers (RCNH⁺NCR). The power law temperature dependencies of the recombination coefficients, α_e, over the temperature range 180 to 600 K for the protonated ions are α_e(T)(cm³ s⁻¹)=3.5±0.5×10⁻⁷ (300/T)^1.38 for HCNH⁺, α_e(T)=3.4±0.5×10⁻⁷ (300/T)^1.03 for CH₃CNH⁺, and α_e(T)=4.6±0.7×10⁻⁷ (300/T)^0.81 for CH₃CH₂CNH⁺. The equivalent values for the proton-bound dimers are α_e(T)(cm³ s⁻¹)=2.4±0.4×10⁻⁶(300/T)^0.5 for (HCN)₂H⁺ to α_e(T)=2.8±0.4×10⁻⁶(300/T)^0.5 for (CH₃CN)₂H⁺, and α_e(T)=2.3±0.3×10⁻⁶(300/T)^0.5 for (CH₃CH₂CN)₂H⁺. The relevance of these data to molecular synthesis in the interstellar medium and the Titan ionosphere are discussed.     

A theoretical investigation into the trapping of noble gases by clathrates on Titan

In this paper, we use a statistical thermodynamic approach to quantify the efficiency with which clathrates on the surface of Titan trap noble gases. We consider different values of the Ar, Kr, Xe, CH₄, C₂H₆ and N₂ abundances in the gas phase that may be representative of Titan's early atmosphere. We discuss the effect of the various parameters that are chosen to represent the interactions between the guest species and the ice cage in our calculations. We also discuss the results of varying the size of the clathrate cages. We show that the trapping efficiency of clathrates is high enough to significantly decrease the atmospheric concentrations of Xe and, to a lesser extent, of Kr, irrespective of the initial gas phase composition, provided that these clathrates are abundant enough on the surface of Titan. In contrast, we find that Ar is poorly trapped in clathrates and, as a consequence, that the atmospheric abundance of argon should remain almost constant. We conclude that the mechanism of trapping noble gases via clathration can explain the deficiency in primordial Xe and Kr observed in Titan's atmosphere by Huygens, but that this mechanism is not sufficient to explain the deficiency in Ar.     

Gas trapping in water ice at very low deposition rates and implications for comets

The effect of water ice formation temperature and rate of ice deposition on a cold plate on the amount of trapped argon (equivalent to CO), and the ratios of Ar/Kr/Xe trapped in the water ice were studied at 50, 27 and 22 K and at ice formation rates ranging over four orders of magnitude, from 10⁻¹ to 10⁻⁵ μm min⁻¹. Contrary to our previous conclusions that cometary ices were formed at 50-60 K, we now conclude that these ices were formed at about 25 K. At 25 K the enrichment ratios for Ar, Kr, and Xe remained the same as those at 50 K, reinforcing our suggestion of cometary contribution of these noble gases to the atmospheres of Earth and Mars.     

Trapping of noble gases in proton-irradiated silicate smokes

Abstract— We have measured Ne, Ar, Kr and Xe in Si₂O₃ “smokes” that were condensed on Al substrates, vapor-deposited with various mixtures of CH₄, NH₃, H₂O and noble gases at 10 K and subsequently irradiated with 1 MeV protons to simulate conditions during grain mantle formation in interstellar clouds. The noble gases were analyzed using conventional stepwise heating and static noble gas mass spectrometry. Neither Ne nor Ar is retained by the samples upon warming to room temperature, but Xe is very efficiently trapped and retained. Kr is somewhat less effectively retained, typically depleted by factors of about 10–20 relative to Xe. Isotopic fractionation favoring the heavy isotopes of Xe and Kr of about 5–10‰/amu is observed. Correlations between the specific chemistry of the vapor deposition and heavy noble gas retention are most likely the result of competition by the various species for irradiation-produced trapping sites. The concentration of Xe retained by some of these smokes exceeds that observed in phase Q of meteorites and, like phase Q, they do not seem to be carriers of the light noble gases. Such artificially prepared material may, therefore, offer clues concerning the incorporation of the heavy planetary noble gases in meteoritic material and the nature of phase Q.     

Neutron Capture Isotopes in the Martian Regolith and Implications for Martian Atmospheric Noble Gases

Impact-produced glasses in some martian meteorites have trapped significant amounts of the recent martian atmosphere. From literature data, we estimate that ∼9% of the trapped ⁸⁰Kr in these meteorites was produced from neutron capture on ⁷⁹Br. Estimates of neutron fluences made from ⁸⁰Kr and ¹⁴⁹Sm for bulk samples of meteorite EET79001 indicate that ⁸⁰Kr excesses in the impact glass were not produced in situ. Theoretical calculations independently predict production of a large neutron-capture component of ⁸⁰Kr and ³⁶Ar in the martian regolith, and part of this component presumably escaped into the martian atmosphere. These calculations were made by using the Los Alamos High-Energy Transport Code to calculate the fluxes of galactic cosmic ray (GCR)-produced thermal neutrons as a function of depth in the uppermost 500 g cm⁻² of the martian surface, and by adopting average Cl, Br, and I concentrations of the upper martian surface of ∼0.3%, ∼20 ppm, and ∼0.5 ppm, respectively. Combining these data with the appropriate neutron-capture cross sections, we calculate Mars global production rates of ⁸⁰Kr_n=2.4×10¹⁶atoms sec⁻¹, ³⁶Ar_n=5.5×10¹⁸ atoms sec⁻¹, and ¹²⁸Xe_n=3×10¹³ atoms sec⁻¹. Calculated global production rates of spallogenic ⁸⁰Kr_sp, and ³⁶Ar_sp, are smaller by factors of ∼770 and ∼29, respectively. It would require ∼330 Myr to produce an amount of ⁸⁰Kr_n equivalent to the amount inferred to be present today in the martian atmosphere (∼2.5×10³² atoms). Production of these neutron-capture components probably has occurred over the past ∼4 Gyr, as only an atmospheric pressure substantially higher than today's would appreciably decrease the neutron flux in the regolith. Thus, most of the neutron-capture noble gases produced over time probably remain in the martian regolith and would make sensitive indicators of the time period a sample has resided near the martian surface. Assuming mixing of the martian surface to an average depth of 100 m, the predicted average regolith concentrations of ⁸⁰Kr_n, ³⁶Ar_n, and ¹²⁸Xe_n are ∼4×10⁻⁹ cm⁻³ g⁻¹, ∼1×10⁻⁶ cm³ g⁻¹, and ∼5×10⁻¹² cm³ g⁻¹, respectively. If similar fractions of these neutron-capture isotopes have escaped into the atmosphere, they would comprise ∼3% and ∼0.2% of the present atmospheric inventories of ³⁶Ar and ¹²⁸Xe, respectively. The fractional excess of ⁸⁰Kr_n in ancient martian meteorite ALH84001 appears similar to that in shock-glass phases of young shergottite meteorites. If ALH84001 acquired its atmospheric gases ∼4 Gyr ago, this implies that, prior to that time, halogens were greatly concentrated at the martian surface by crustal formational and weathering processes, impacts efficiently degassed the regolith, and Mars did not have a significant atmosphere to shield the surface.     

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.     

Devgaon (H3) chondrite: Classification and complex cosmic ray exposure history

Abstract— The Devgaon meteorite fell in India on February 12, 2001 and was immediately collected. It is an ordinary chondrite having a number of SiO₂‐rich objects and some Ca, Al‐rich inclusions. Olivines (Fa_17–19) are fairly equilibrated, while pyroxenes (Fs_4–20) are unequilibrated. Occasionally, shock veins are visible, but the bulk rock sample is very weakly shocked (S2). Chondrules and chondrule fragments are abundant. Based on chemical and petrological features, Devgaon is classified as an H3.8 group chondrite. Several cosmogenic radionuclides ranging in half‐lives from 5.6 d (⁵²Mn) to 7.3 times 10⁵ yr (²⁶Al), noble gases (He, Ne, Ar, Kr, and Xe), and particle track density have been measured. The track density in olivines from five spot samples varies between (4.6 to 9) × 10⁶ cm^?2 showing a small gradient within the meteorite. The light noble gases are dominated by cosmogenic and radiogenic components. Large amounts of trapped gases (Ar, Kr, and Xe) are present. In addition, (n, γ) products from Br and I are found in Kr and Xe, respectively. The average cosmic ray exposure age of 101 ± 8 Ma is derived based on cosmogenic ³⁸Ar, ⁸³Kr, and ¹²⁶Xe. The track production rates correspond to shielding depths of about 4.9 to 7.8 cm, indicating that the stone suffered type IV ablation. Low ⁶⁰Co, high (²²Ne/²¹Ne)_c, and large neutron produced excesses at ⁸⁰Kr, ⁸²Kr, and ¹²⁸Xe indicate a complex exposure history of the meteoroid. In the first stage, a meter‐sized body was exposed for nearly 10⁸ yr in the interplanetary space that broke up in ?50 cm‐sized fragments about a million years ago (stage 2), before it was captured by the Earth.     

Extreme Ultraviolet Photon-Induced Chemical Reactions in the C2H2-H2O Mixed Ices at 10 K

Experimental results on the spectral identification of new infrared absorption features and the changes of their absorbances produced through vacuum ultraviolet-extreme ultraviolet (VUV-EUV) photon-induced chemical reactions in the C₂H₂-H₂O mixed ices at 10 K are obtained. To the best of our knowledge, this is the first time that EUV photons have been employed in the study of the photolysis of ice analogues. Two different compositions, i.e., C₂H₂:H₂O=1:4 and 1:1, were investigated in this work. A tunable intense synchrotron radiation light source available at the Synchrotron Radiation Research Center, Hsinchu, Taiwan, was employed to provide the required VUV-EUV photons. In this study, the photon wavelengths selected to irradiate the icy samples corresponded to the prominent solar hydrogen, helium, and helium ion lines at 121.6 nm, 58.4 nm, and 30.4 nm, respectively. The photon dosages used were typically in the range of 1×10¹⁵ to 2×10¹⁷ photons. Molecular species produced and identified in the ice samples at 10 K resulting from VUV-EUV photon irradiation are mainly CO, CO₂, CH₄, C₂H₆, CH₃OH, and H₂CO. In addition to several unidentified features, we have tentatively assigned several absorption features to HCO, C₃H₈, and C₂H₅OH. While new molecular species were formed, the original reactants, i.e., H₂O and C₂H₂, were detectably depleted due to their conversion to other species. The new chemical species produced by irradiation of photons at 30.4 nm and 58.4 nm can be different from those produced by the 121.6-nm photolysis. In general, the product column density of CO reaches saturation at a lower photon dosage than that of CO₂. Furthermore, the production yield of CO is higher than that of CO₂ in the photon irradiation. In the present study, we also observe that the photon-induced chemical reaction yields are high using photons at 30.4 and 58.4 nm. The results presented in this work are essential to our understanding of chemical synthesis in ice analogues, e.g., the cometary-type ices and icy satellites of planetary systems.