Formation of methane in comet impacts: implications for Earth, Mars, and Titan

We calculate the amount of methane that may form via reactions catalyzed by metal-rich dust that condenses in the wake of large cometary impacts. Previous models of the gas-phase chemistry of impacts predicted that the terrestrial planets' atmospheres should be initially dominated by CO/CO₂, N₂, and H₂O. CH₄ was not predicted to form in impacts because gas-phase reactions in the explosion quench at temperatures ∼2000 K, at which point all of the carbon is locked in CO. We argue that the dust that condenses out in the wake of a large comet impact is likely to have very effective catalytic properties, opening up reaction pathways to convert CO and H₂ to CH₄ and CO₂, at temperatures of a few hundred K. Together with CO₂, CH₄ is an important greenhouse gas that has been invoked to compensate for the lower luminosity of the Sun ∼4 Gyr ago. Here, we show that heterogeneous (gas-solid) reactions on freshly-recondensed dust in the impact cloud may provide a plausible nonbiological mechanism for reducing CO to CH₄ before and during the emergence of life on Earth, and perhaps Mars as well. These encouraging results emphasize the importance of future research into the kinetics and catalytic properties of astrophysical condensates or “smokes” and also more detailed models to determine the conditions in impact-generated dust clouds.     

Kamacite sulfurization in the solar nebula

Abstract— The kinetics and mechanisms of kamacite sulfurization were studied experimentally at temperatures and H₂S/H₂ ratios relevant to the solar nebula. Pieces of the Canyon Diablo meteorite were heated at 558 K, 613 K, and 643 K in 50 parts per million by volume (ppmv) H₂S-H₂ gas mixtures for up to one month. Optical microscopy and x-ray diffraction analyses show that the morphology and crystal orientation of the resulting sulfide layers vary with both time and temperature. Electron microprobe analyses reveal three distinct phases in the reaction products: monosulfide solid solution (mss), (Fe, Ni, Co)_1-xS, pentlandite (Fe, Ni, Co)_9-xS₈, and a P-rich phase. The bulk composition of the remnant metal was not significantly changed by sulfurization. Kamacite sulfurization at 558 K followed parabolic kinetics for the entire duration of the experiments. Sulfide layers that formed at 613 K grew linearly with time, while those that formed at 643 K initially grew linearly with time then switched to parabolic kinetics upon reaching a critical thickness. The experimental results suggest that a variety of thermodynamic, kinetic, and physical processes control the final composition and morphology of the sulfide layers. We combine morphological, x-ray diffraction, electron microprobe, and kinetic data to produce a comprehensive model of sulfide formation in the solar nebula. Then, we present a set of criteria to assist in the identification of solar nebula condensate sulfides in primitive meteorites.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

Dependence of the effective rate constants for the hydrogenation of CO on the temperature and composition of the surface

Experiments on the hydrogenation of CO on pure CO and CO-H₂O mixed ice have been performed at temperatures between 8 and 20 K. We obtained temperature and compositional dependence of the effective reaction rate constants. Results indicate that hydrogenation proceeds efficiently on pure solid CO and CO-H₂O mixed ice at temperatures below 10 and 20 K, respectively. Rate constants for pure CO decreased significantly at 12 K compared to those obtained with CO-H₂O mixed ice. Hydrogenation of CO at temperatures greater than 12 K were catalyzed by the H₂O adjacent to the CO. The importance of the experimental results for some relevant astrophysical environments has also been outlined.     

Evaporation of nebular fines during chondrule formation

Studies of matrix in primitive chondrites provide our only detailed information about the fine fraction (diameter <2 μm) of solids in the solar nebula. A minor fraction of the fines, the presolar grains, offers information about the kinds of materials present in the molecular cloud that spawned the Solar System. Although some researchers have argued that chondritic matrix is relatively unaltered presolar matter, meteoritic chondrules bear witness to multiple high-temperature events each of which would have evaporated those fines that were inside the high-temperature fluid. Because heat is mainly transferred into the interior of chondrules by conduction, the surface temperatures of chondrules were probably at or above 2000 K. In contrast, the evaporation of mafic silicates in a canonical solar nebula occurs at around 1300 K and FeO-rich, amorphous, fine matrix evaporates at still lower temperatures, perhaps near 1200 K. Thus, during chondrule formation, the temperature of the placental bath was probably >700 K higher than the evaporation temperatures of nebular fines. The scale of chondrule forming events is not known. The currently popular shock models have typical scales of about ¹⁰⁵ km. The scale of nebular lightning is less well defined, but is certainly much smaller, perhaps in the range 1 to 1000 m. In both cases the temperature pulses were long enough to evaporate submicrometer nebular fines. This interpretation disagrees with common views that meteoritic matrix is largely presolar in character and CI-chondrite-like in composition. It is inevitable that presolar grains (both those recognized by their anomalous isotopic compositions and those having solar-like compositions) that were within the hot fluid would also have evaporated. Chondrule formation appears to have continued down to the temperatures at which planetesimals formed, possibly around 250 K. At temperatures >600 K, the main form of C is gaseous CO. Although the conversion of CO to CH₄ at lower temperatures is kinetically inhibited, radiation associated with chondrule formation would have accelerated the conversion. There is now evidence that an appreciable fraction of the nanodiamonds previously held to be presolar were actually formed in the solar nebula. Industrial condensation of diamonds from mixtures of CH₄ and H₂ implies that high nebular CH₄/CO ratios favored nanodiamond formation. A large fraction of chondritic insoluble organic matter may have formed in related processes. At low nebular temperatures appreciable water should have been incorporated into the smoke that condensed following dust (and some chondrule) evaporation. If chondrule formation continued down to temperatures as low as 250 K this process could account for the water concentration observed in primitive chondrites such as LL3.0 and CO3.0 chondrites. Higher H₂O contents in CM and CI chondrites may reflect asteroidal redistribution. In some chondrite groups (e.g., CR) the Mg/Si ratio of matrix material is appreciably (30%) lower than that of chondrules but the bulk Mg/Si ratio is roughly similar to the CI or solar ratio. This has been interpreted as a kind of closed-system behavior sometimes called “complementarity.” This leads to the conclusion that nebular fines were efficiently agglomerated. Its importance, however is obscured by the observation that bulk Mg/Si ratios in ordinary and enstatite chondrites are much lower than those in carbonaceous chondrites, and thus that complementarity did not hold throughout the solar nebula.     

Phase transitions of α-quartz at elevated temperatures under dynamic compression using a membrane-driven diamond anvil cell: Clues to impact cratering?

Coesite and stishovite are high-pressure silica polymorphs known to have been formed at several terrestrial impact structures. They have been used to assess pressure and temperature conditions that deviate from equilibrium formation conditions. Here we investigate the effects of nonhydrostatic, dynamic stresses on the formation of high-pressure polymorphs and the amorphization of α-quartz at elevated temperatures. The obtained disequilibrium states are compared with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We analyzed phase transformations starting with α-quartz in situ under dynamic loading utilizing a membrane-driven diamond anvil cell. Using synchrotron powder X-ray diffraction, the phase transitions of SiO₂ are identified up to 77.2 GPa and temperatures of 1160 K at compression rates ranging between 0.10 and 0.37 GPa s⁻¹. Coesite starts forming above 760 K in the pressure range between 2 and 11 GPa. At 1000 K, coesite starts to transform to stishovite. This phase transition is not completed at 1160 K in the same pressure range. Therefore, the temperature initiates the phase transition from α-quartz to coesite, and the transition from coesite to stishovite. Below 1000 K and during compression, α-quartz becomes amorphous and partially converts to stishovite. This phase transition occurs between 25 and 35 GPa. Above 1000 K, no amorphization of α-quartz is observed. High temperature experiments reveal the strong thermal dependence of the formation of coesite and stishovite under nonhydrostatic and disequilibrium conditions.     

Letter to the Editor: The collisional broadening of carbon radio recombination lines

The density matrix equations of highly excited carbon are analytically solved as functions of line number and temperature. Allowing for the series of the impact approximation theory and quadrupole interaction potential, the line widths are found with the theoretical error less than 0.06 in the range of temperatures T _e = 25 − 100 K. To determine the medium temperature and density by using the experimental values of line widths, the Doppler, radiational and impact broadening are calculated for the lines with the principal quantum numbers n > 300. This revised version was published online in July 2006 with corrections to the Cover Date.     

Observed heating effects of conjugate photoelectrons

A gridded spherical electrostatic analyzer aboard Injun 5 has been used to measure fluxes of thermal and hyperthermal electrons at subauroral latitudes in the midnight sector of the northern ionosphere between altitudes of 2500 and 850 km. Due to the offset between the geomagnetic and geographic poles hyperthermal fluxes, consisting of energetic photoelectrons that have escaped from the sunlit southern hemisphere are observed along orbits over the Atlantic Ocean and North America but not over Asia. The ambient electron temperatures (T_e) near 2500 km have their highest values at trough latitudes for all longitudes. At altitudes near 1000 km elevated electron temperatures in the trough were not a consistent feature of the data. Equatorward of the trough, in the longitude sector to which conjugate photoelectrons have access, T_e ～ 4000 K at 2500 km and ～ 3000 K at 1000 km. For regions with the conjugate point in darkness T_e ? 2300 K over the 1000–2500 km altitude range. The effective thermal characteristics of conjugate photoelectrons are studied as functions of altitude and latitude. The observations indicate that (1) at trough latitudes elevated electron temperatures in the topside ionosphere are mostly produced by sources other than conjugate photoelectrons, and (2) at subtrough latitudes, in the Alantic Ocean-North American longitude sector, conjugate photoelectrons contribute significantly to the heating of topside electrons. Much of the conjugate photoelectron energy is deposited at altitudes >2500 km then conducted along magnetic field lines into the ionosphere.     

Longevity of fluorine-bearing tremolite on Venus

There is a general belief that hydrous minerals cannot exist on Venus under current surface conditions. This view was challenged when Johnson and Fegley (2000, Icarus 146, 301-306) showed that tremolite (Ca₂Mg₅Si₈O₂₂(OH)₂), a hydrous mineral, is stable against thermal decomposition at current Venus surface temperatures, e.g., 50% decomposition in 4 Ga at 740 K. To further explore hydrous mineral thermal stability on Venus, we experimentally determined the thermal decomposition kinetics of fluorine-bearing tremolite. Fluor-tremolite is thermodynamically more stable than OH-tremolite and should decompose more slowly. However how much slower was unknown. We measured the decomposition rate of fluorine-bearing tremolite and show that its decomposition is several times to greater than ten times slower than that of OH-tremolite. We also show that F-bearing tremolite is depleted in fluorine after decomposition and that fluorine is lost as a volatile species such as HF gas. If tremolite ever formed on Venus, it would probably also contain fluorine. The exceptional stability of F-bearing tremolite strengthens our conclusions that if hydrous minerals ever formed on Venus, they could still be there today.     

Limits on the trapping of atmospheric CH4 in martian polar ice analogs

Recent detection of methane (CH₄) on Mars has generated interest in possible biological or geological sources, but the factors responsible for the reported variability are not understood. Here we explore one potential sink that might affect the seasonal cycling of CH₄ on Mars - trapping in ices deposited on the surface. Our apparatus consisted of a high-vacuum chamber in which three different Mars ice analogs (water, carbon dioxide, and carbon dioxide clathrate hydrates) were deposited in the presence of CH₄ gas. The ices were monitored for spectroscopic evidence of CH₄ trapping using transmission Fourier-Transform Infrared (FT-IR) spectroscopy, and during subsequent sublimation of the ice films the vapor composition was measured using mass spectrometry (MS). Trapping of CH₄ in water ice was confirmed at deposition temperatures <100 K which is consistent with previous work, thus validating the experimental methods. However, no trapping of CH₄ was observed in the ice analogs studied at warmer temperatures (140 K for H₂O and CO₂ clathrate, 90 K for CO₂ snow) with approximately 10 mTorr CH₄ in the chamber. From experimental detection limits these results provide an upper limit of 0.02 for the atmosphere/ice trapping ratio of CH₄. If it is assumed that the trapping mechanism is linear with CH₄ partial pressure and can be extrapolated to Mars, this upper limit would indicate that less than 1% is expected to be trapped from the largest reported CH₄ plume, and therefore does not represent a significant sink for CH₄.     

Experimental constraints on alkali condensation in chondrule formation

Abstract— To assess whether the alkali behavior observed in chondrules of primitive meteorites is attributable to volatilization from the raw materials of chondrules during chondrule formation events or attributable to condensation processes from the nebular gas, we set up a new experimental device able to expose silicate melt samples to a controlled alkali partial pressure at high temperature under fixed O fugacity. Using a mixture of potassium carbonate (K₂CO₃) and graphite (C) as the source of the K gas (K_g), we studied the condensation kinetics of K and its solubility in CaO‐MgO‐Al₂O₃‐SiO₂ silicate melts, according to the reaction 2 K _(g) + 1/2 _(g) = K₂O _(melt) From these results, we show that alkali entering in chondrules from the nebular gas is a viable mechanism to explain the chondrules alkali contents and their δ⁴¹K‐isotopic signatures, at timescales relevant to chondrule formation. Finally, we also suggest that chondrules may have formed in non‐canonical nebular environments and that the flash‐heating scenario is not a prerequisite to chondrule formation.     

Ferrous silicate spherules with euhedral iron‐nickel metal grains from CH carbonaceous chondrites: Evidence for supercooling and condensation under oxidizing conditions

Abstract— The CH carbonaceous chondrites contain a population of ferrous (Fe/(Fe + Mg) ? 0.1‐0.4) silicate spherules (chondrules), about 15–30 μm in apparent diameter, composed of cryptocrystalline olivinepyroxene normative material, ±SiO₂‐rich glass, and rounded‐to‐euhedral Fe, Ni metal grains. The silicate portions of the spherules are highly depleted in refractory lithophile elements (CaO, Al₂O₃, and TiO₂ <0.04 wt%) and enriched in FeO, MnO, Cr₂O₃, and Na₂O relative to the dominant, volatile‐poor, magnesian chondrules from CH chondrites. The Fe/(Fe + Mg) ratio in the silicate portions of the spherules is positively correlated with Fe concentration in metal grains, which suggests that this correlation is not due to oxidation, reduction, or both of iron (FeO_sil ? Fe_met) during melting of metal‐silicate solid precursors. Rather, we suggest that this is a condensation signature of the precursors formed under oxidizing conditions. Each metal grain is compositionally uniform, but there are significant intergrain compositional variations: about 8–18 wt% Ni, <0.09 wt% Cr, and a sub‐solar Co/Ni ratio. The precursor materials of these spherules were thus characterized by extreme elemental fractionations, which have not been observed in chondritic materials before. Particularly striking is the fractionation of Ni and Co in the rounded‐to‐euhedral metal grains, which has resulted in a Co/Ni ratio significantly below solar. The liquidus temperatures of the euhedral Fe, Ni metal grains are lower than those of the coexisting ferrous silicates, and we infer that the former crystallized in supercooled silicate melts. The metal grains are compositionally metastable; they are not decomposed into taenite and kamacite, which suggests fast postcrystallization cooling at temperatures below 970 K and lack of subsequent prolonged thermal metamorphism at temperatures above 400–500 K.     

Evaporation effects on the formation of martian gullies

In order to investigate the formation of martian gullies and the stability of fluids on Mars, we examined about 120 gully images. Twelve HiRISE images contained a sufficient number of Transverse Aeolian Ridges (TARs) associated with the gullies to make the following measurements: overall gully length, length of the alcove, channel and apron, and we also measured the frequency of nearby TARs. Six of the 12 images examined showed a statistically significant negative correlation between overall gully length (alcove, channel and apron length) and TAR frequency. Previous experimental work from our group has shown that at temperatures below ∼200 K, evaporation rate increases by about an order of magnitude as wind speed increases from 0 to ∼15 m/s. Thus the negative correlations we observe between gully length and dune frequency can be explained by formation at temperatures below ∼200 K where wind speed/evaporation is a factor governing gully length. In these cases evaporation of the fluid carving the gully was a constraint on their dimensions. Cases where there is no correlation between gully length and TAR frequency, can be explained by formation at temperatures >200 K. The temperatures are consistent with Global Circulation Model and Thermal Emission Spectrometer (TES) data for these latitudes. The temperatures suggested by these trends are consistent with the fluid responsible for gully formation being a strong brine, such as Fe₂(SO₄)₃ which has a eutectic temperature of ∼200 K. We also find that formation timescales for gullies are 10⁵-10⁶ years.     

The greenhouse of Titan

Both non-gray radiative equilibrium and gray convective equilibrium calculations for Titan indicate that the discrepancy between the equilibrium temperature of an atmosphereless Titan and the observed infrared temperatures can be explained by a massive molecular hydrogen greenhouse effect. The convective calculations indicate a probable minimum optical depth of 14, corresponding to many tens of km-atm of H₂, and total pressures of ～0.1 bar. The tropopause is several hundred km above the Titanian surface and at a temperature of about 90°K. Methane condensation is likely at this level. Such an atmosphere is unstable against atmospheric blow-off unless typical mesosphere scale heights are < 25km, an unlikely situation. Blow-off can also be circumvented by exospheric temperatures near the freezing point of hydrogen. It is considered more plausible that the present atmosphere is in equilibrium between outgassing and blow-off of the one hand and accretion from protons trapped in a hypothetical Saturnian magnetic field on the other; or exhibits uncompensated blow-off of outgassing products. To maintain the present blow-off rate without compensation for all of geological time requires an outgassing equivalent to the volatilization of a few km of subsurface ices. Photo-dissociation of these volatilized ices produces the observed high abundance of H₂ as well as large quantities of complex organic chromophores which may explain the reddish coloration of the Titanian cloud deck. An extensive circum-Titanian hydrogen corona is postulated. Surface temperatures as high as 200°K are not excluded. Because of its high temperatures and pressures and the probable large abundance of organic compounds, Titan is a prime target for spacecraft exploration in the outer solar system.     

Observations of metallic species in Mercury’s exosphere

From observations of the metallic species sodium (Na), potassium (K), and magnesium (Mg) in Mercury’s exosphere, we derive implications for source and loss processes. All metallic species observed exhibit a distribution and/or line width characteristic of high to extreme temperature - tens of thousands of degrees K. The temperatures of refractory species, including magnesium and calcium, indicate that the source process for the atoms observed in the tail and near-planet exosphere are consistent with ion sputtering and/or impact vaporization of a molecule with subsequent dissociation into the atomic form. The extended Mg tail is consistent with a surface abundance of 5-8% Mg by number, if 30% of impact-vaporized Mg remains as MgO and half of the impact vapor condenses. Globally, ion sputtering is not a major source of Mg, but locally the sputtered source can be larger than the impact vapor source. We conclude that the Na and K in Mercury’s exosphere can be derived from a regolith composition similar to that of Luna 16 soil (or Apollo 17 orange glass), in which the abundance by number is 0.0027 (0.0028) for Na and 0.0006 (0.0045) for K.     

Intrinsic properties of carbon stars. I. Effective temperature scale of N-type carbon stars

It is shown that the infrared flux method for determining stellar effective temperatures (Blackwell and Shallis 1977; Blackwell, Petford and Shallis 1980) can be applied to cool carbon stars. Although the spectra of cool carbon stars are highly line blanketed, the spectral region between 3 and 4 μm (L-band in the infrared photometry system) is found to be relatively free from strong line absorption. The ratioR _L of bolometric flux toL flux can then be used as a measure of effective temperature. On the basis of the predicted line-blanketed flux based on model atmospheres, with an empirical correction for the effect of 3 μm absorption due to polyatomic species (HCN, C₂H₂), it is shown thatR _L is roughly proportional to T³ _eff. The high sensitivity ofR _L to T_eff makes it a very good measure of effective temperature, and the usual difficulty due to differential line blanketing effect in the analyses of photometric indices of cool carbon stars can be minimized. It is found that the majority of N-type carbon stars with small variability (SRb and Lb variables) are confined to the effective temperature range between 2400 and 3200 K, in contrast to M-giant stars (M0 III - M6 III, including SRb and Lb variables) that are confined to the effective temperature range between 3200 and 3900 K. The effective temperatures based on the infrared flux method show good agreement with those derived directly from angular diameter measurements of 5 carbon stars. On the basis of the new effective temperature scale for carbon stars, it is shown that the well known C-classification does not represent a temperature sequence. On the other hand, colour temperatures based on various photometric indices all show good correlations with our derived effective temperatures. An erratum to this article is available at .     

Spectrophotometry of three planetary nebulae

The results of a spectroscopic investigation of three possible planetary nebulae, K4- 53, K4- 55, and K4- 57, are presented. It is shown that K4- 53 and K4- 55 are planetary nebulae while K4- 57 can be considered with high probability to be one. The temperatures of the nuclei of these nebulae are determined by Ambartsumian’s method. The optical depths for L_c photons in the region of λ ≤ 912 Å are determined. An anomalously high nitrogen abundance is observed in K4- 55.     

Evidence for K‐rich terranes on Vesta from impact spherules

Abstract— The howardite‐eucrite‐diogenite (HED) clan is a group of meteorites that probably originate from the asteroid Vesta. Some of them are complex breccias that contain impact glasses whose compositions mirror that of their source regions. Some K‐rich impact glasses (up to 2 wt% K₂O) suggest that in addition to basalts and ultramafic cumulates, K‐rich rocks are exposed on Vesta's surface. One K‐rich glass (up to 6 wt% K₂O), with a felsic composition, provides the first evidence of highly differentiated K‐rich rocks on a large asteroid. They can be compared to the rare lunar granites and suggest that magmas generated in a large asteroid are more diverse than previously thought.     

A new model of the hydrogen and helium-broadened microwave opacity of ammonia based on extensive laboratory measurements

Close to 2000 laboratory measurements of the microwave opacity and refractivity of gaseous NH₃ in an H₂/He atmosphere have been conducted in the 1.1-20 cm wavelength range (1.5-27 GHz) at pressures from 30 mbar to 12 bar and at temperatures from 184 to 450 K. The mole fraction of NH₃ ranged from 0.06 to 6% with some additional measurements of pure NH₃. The high accuracy of these results have enabled development of a new model for the opacity of NH₃ in a H₂/He atmosphere under jovian conditions. The model employs the Ben-Reuven lineshape applied to the published inversion line center frequencies and intensities of NH₃ (JPL Catalog—[Pickett, H.M., Poynter, R.L., Cohen, E.A., Delitsky, M.L., Pearson, J.C., Müller, H.S.P., 1998. J. Quant. Spectrosc. Radiat. Trans. 60, 883-890]) with empirically-fitted line parameters for H₂ and He broadening, and for the self-broadening of some previously unmeasured ammonia inversion lines. The new model for ammonia opacity will provide reliable results for temperatures from 150 to 500 K, at pressures up to 50 bar and at frequencies up to 40 GHz. These results directly impact the retrieval of jovian atmospheric constituent abundances from the Galileo Probe radio signal absorption measurements, from microwave emission measurements conducted with Earth-based radio telescopes and with the future NASA Juno mission, and studies of Saturn's atmosphere conducted with the Cassini Radio Science Experiment and the Cassini RADAR 2.1 cm passive radiometer.     

The role of Fischer-Tropsch catalysis in the origin of methane-rich Titan

Fischer-Tropsch catalysis, which converts CO and H₂ into CH₄ on the surface of iron catalyst, has been proposed to produce the CH₄ on Titan during its formation process in a circum-planetary subnebula. However, Fischer-Tropsch reaction rate under the conditions of subnebula have not been measured quantitatively yet. In this study, we conduct laboratory experiments to determine CH₄ formation rate and also conduct theoretical calculation of clathrate formation to clarify the significance of Fischer-Tropsch catalysis in a subnebula. Our experimental result indicates that the range of conditions where Fischer-Tropsch catalysis proceeds efficiently is narrow (T∼500-600 K) in a subnebula because the catalysts are poisoned at temperatures above 600 K under the condition of subnebula (i.e., H₂/CO = 1000). This suggests that an entire subnebula may not become rich in CH₄ but rather that only limited region of a subnebula may enriched in CH₄ (i.e., CH₄-rich band formation). Our experimental result also suggests that both CO and CO₂ are converted into CH₄ within time significantly shorter than the lifetime of the solar nebula at the optimal temperatures around 550 K. The calculation result of clathration shows that CO₂-rich satellitesimals are formed in the catalytically inactive outer region of subnebula. In the catalytically active inner region, CH₄-rich satellitesimals are formed. The resulting CH₄-rich satellitesimals formed in this region play an important role in the origin of CH₄ on Titan. When our experimental data are applied to a high-pressure model for subnebula evolution, it would predict that there should be CO₂ underneath the Iapetus subsurface and no thick CO₂ ice layer on Titan's icy crust. Such surface and subsurface composition, which may be observed by Cassini-Huygens mission, would provide crucial information on the origin of icy satellites.