We describe a scenario of Titan's formation matching the constraints imposed by its current atmospheric composition. Assuming that the abundances of all elements, including oxygen, are solar in the outer nebula, we show that the icy planetesimals were agglomerated in the feeding zone of Saturn from a mixture of clathrates with multiple guest species, so-called stochiometric hydrates such as ammonia hydrate, and pure condensates. We also use a statistical thermodynamic approach to constrain the composition of multiple guest clathrates formed in the solar nebula. We then infer that krypton and xenon, that are expected to condense in the 20-30 K temperature range in the solar nebula, are trapped in clathrates at higher temperatures than 50 K. Once formed, these ices either were accreted by Saturn or remained embedded in its surrounding subnebula until they found their way into the regular satellites growing around Saturn. In order to explain the carbon monoxide and primordial argon deficiencies of Titan's atmosphere, we suggest that the satellite was formed from icy planetesimals initially produced in the solar nebula and that were partially devolatilized at a temperature not exceeding ∼ 50 K during their migration within Saturn's subnebula. The observed deficiencies of Titan's atmosphere in krypton and xenon
We use a statistical thermodynamic approach to determine the composition of clathrate hydrates which may form from a multiple compound gas whose composition is similar to that of Titan's atmosphere. Assuming that noble gases are initially present in this gas phase, we calculate the ratios of xenon, krypton and argon to species trapped in clathrate hydrates. We find that these ratios calculated for xenon and krypton are several orders of magnitude higher than in the coexisting gas at temperature and pressure conditions close to those of Titan's present atmosphere at ground level. Furthermore we show that, by contrast, argon is poorly trapped in these ices. This trapping mechanism implies that the gas-phase is progressively depleted in xenon and krypton when the coexisting clathrate hydrates form whereas the initial abundance of argon remains almost constant. Our results are thus compatible with the deficiency of Titan's atmosphere in xenon and krypton measured by the Huygens probe during its descent on January 14, 2005. However, in order to interpret the subsolar abundance of primordial Ar also revealed by Huygens, other processes that occurred either during the formation of Titan or during its evolution must be also invoked.
Recent observations have evidenced traces of methane (CH 4 ) heterogeneously distributed in the martian atmosphere. However, because the lifetime of CH 4 in the atmosphere of Mars is estimated to be around 300-600 years on the basis of photochemistry, its release from a subsurface reservoir or an active primary source of methane have been invoked in the recent literature. Among the existing scenarios, it has been proposed that clathrate hydrates located in the near subsurface of Mars could be at the origin of the small quantities of the detected CH 4 . Here, we accurately determine the composition of these clathrate hydrates, as a function of temperature and gas phase composition, by using a hybrid statistical thermodynamic model based on experimental data. Compared to other recent works, our model allows us to calculate the composition of clathrate hydrates formed from a more plausible composition of the martian atmosphere by considering its main compounds, i.e. carbon dioxyde, nitrogen and argon, together with methane. Besides, because there is no low temperature restriction in our model, we are able to determine the composition of clathrate hydrates formed at temperatures corresponding to the extreme ones measured in the polar caps. Our results show that methane enriched clathrate hydrates could be stable in the subsurface of Mars only if a primitive CH 4 -rich atmosphere has existed or if a subsurface source of CH 4 has been (or is still) present.
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