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1.
Eric Chassefière 《Icarus》2009,204(1):137-271
The observations of methane made by the PFS instrument onboard Mars Express exhibit a definite correlation between methane mixing ratio, water vapor mixing ratio, and cloud optical depth. The recent data obtained from ground-based telescopes seem to confirm the correlation between methane and water vapor. In order to explain this correlation, we suggest that the source of gaseous methane is atmospheric, rather than at the solid surface of the planet, and that this source may consist of metastable submicronic particles of methane clathrate hydrate continuously released to the atmosphere from one or several clathrate layers at depth, according to the phenomenon of “anomalous preservation” evidenced in the laboratory. These particles, lifted up to middle atmospheric levels due to their small size, and therefore filling the whole atmosphere, serve as condensation nuclei for water vapor. The observed correlation between methane and water vapor mixing ratios could be the signature of the decomposition of the clathrate crystals by condensation-sublimation processes related to cloud activity. Under the effect of water condensation on crystal walls, metastability could be broken and particles be eroded, resulting in a subsequent irreversible release of methane to the gas phase. Using PFS data, and according to our hypothesis, the lifetime of gaseous methane is estimated to be smaller than an upper limit of 6 ± 3 months, much smaller than the lifetime of 300 yr calculated from atmospheric chemical models. The reason why methane has a short lifetime might be the occurrence of heterogeneous chemical decomposition of methane in the subsurface, where it is known since Viking biology experiments that oxidants efficiently decompose organic matter. If true, it is shown by using existing models of H2O2 penetration in the regolith that methane could prevent H2O2 from penetrating in the subsurface, and further oxidizing the soil, at depths larger than a few millimeters. The present source of methane clathrate, acting over the last few hundred thousand or million years, could have given rise to the thin CO2-ice layer covering the permanent water ice south polar cap. The hypothesis proposed in this paper requires, to be validated, a number of laboratory experiments studying the stability of methane clathrates in martian atmospheric conditions, and the kinetics and amplitude of clathrate particle erosion in presence of condensing water vapor. Detailed future observations of methane, and associated modeling, will allow to more accurately quantify the production rate of methane clathrate, its temporal variability at seasonal scale, and possibly to locate the source(s) of clathrates at the surface.  相似文献   

2.
3.
Several substances besides water ice have been detected on the surface of Europa by spectroscopic sensors, including CO2, SO2, and H2S. These substances might occur as pure crystalline ices, as vitreous mixtures, or as clathrate hydrate phases, depending on the system conditions and the history of the material. Clathrate hydrates are crystalline compounds in which an expanded water ice lattice forms cages that contain gas molecules. The molecular gases that may constitute Europan clathrate hydrates may have two possible ultimate origins: they might be primordial condensates from the interstellar medium, solar nebula, or jovian subnebula, or they might be secondary products generated as a consequence of the geological evolution and complex chemical processing of the satellite. Primordial ices and volatile-bearing compounds would be difficult to preserve in pristine form in Europa without further processing because of its active geological history. But dissociated volatiles derived from differentiation of a chondritic rock or cometary precursor may have produced secondary clathrates that may be present now. We have evaluated the current stability of several types of clathrate hydrates in the crust and the ocean of Europa. The depth at which the clathrates of SO2, CO2, H2S, and CH4 are stable have been obtained using both the temperatures observed in the surface [Spencer, J.R., Tamppari, L.K., Martin, T.Z., Travis, L.D., 1999. Temperatures on Europa from Galileo photopolarimeter-radiometer: Nighttime thermal anomalies. Science 284, 1514-1516] and thermal models for the crust. In addition, their densities have been calculated in order to determine their buoyancy in the ocean, obtaining different results depending upon the salinity of the ocean and type of clathrate. For instance, assuming a eutectic composition of the system MgSO4H2O for the ocean, CO2, H2S, and CH4 clathrates would float but SO2 clathrate would sink to the seafloor; an ocean of much lower salinity would allow all these clathrates to sink, except that CH4 clathrate would still float. Many geological processes may be driven or affected by the formation, presence, and destruction of clathrates in Europa such as explosive cryomagmatic activity [Stevenson, D.J., 1982. Volcanism and igneous processes in small icy satellites. Nature 298, 142-144], partial differentiation of the crust driven by its clathration, or the local retention of heat within or beneath clathrate-rich layers because of the low thermal conductivity of clathrate hydrates [Ross, R.G., Kargel, J.S., 1998. Thermal conductivity of Solar System ices, with special reference to martian polar caps. In: Schmitt, B., De Berg, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Dordrecht, pp. 33-62]. On the surface, destabilization of these minerals and compounds, triggered by fracture decompression or heating could result in formation of chaotic terrain morphologies, a mechanism that also has been proposed for some martian chaotic terrains [Tanaka, K.L., Kargel, J.S., MacKinnon, D.J., Hare, T.M., Hoffman, N., 2002. Catastrophic erosion of Hellas basin rim on Mars induced by magmatic intrusion into volatile-rich rocks. Geophys. Res. Lett. 29 (8); Kargel, J.S., Prieto-Ballesteros, O., Tanaka K.L., 2003. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton? Geophys. Res. 5. Abstract 14252]. Models of the evolution of the ice shell of Europa might take into account the presence of clathrate hydrates because if gases are vented from the silicate interior to the water ocean, they first would dissolve in the ocean and then, if the gas concentrations are sufficient, may crystallize. If any methane releases occur in Europa by hydrothermal or biological activity, they also might form clathrates. Then, from both geological and astrobiological perspectives, future missions to Europa should carry instrumentation capable of clathrate hydrate detection.  相似文献   

4.
The origin of Titan’s atmospheric methane is a key issue for understanding the origin of the saturnian satellite system. It has been proposed that serpentinization reactions in Titan’s interior could lead to the formation of the observed methane. Meanwhile, alternative scenarios suggest that methane was incorporated in Titan’s planetesimals before its formation. Here, we point out that serpentinization reactions in Titan’s interior are not able to reproduce the deuterium over hydrogen (D/H) ratio observed at present in methane in its atmosphere, and would require a maximum D/H ratio in Titan’s water ice 30% lower than the value likely acquired by the satellite during its formation, based on Cassini observations at Enceladus. Alternatively, production of methane in Titan’s interior via radiolytic reactions with water can be envisaged but the associated production rates remain uncertain. On the other hand, a mechanism that easily explains the presence of large amounts of methane trapped in Titan in a way consistent with its measured atmospheric D/H ratio is its direct capture in the satellite’s planetesimals at the time of their formation in the solar nebula. In this case, the mass of methane trapped in Titan’s interior can be up to ∼1300 times the current mass of atmospheric methane.  相似文献   

5.
Chia C. Wang  Ruth Signorell 《Icarus》2010,206(2):787-264
Layered methane clouds in Titan’s troposphere with an upper methane ice cloud, a lower liquid methane-nitrogen cloud, and a gap in between were suggested from in situ measurements and ground-based observations. Here we report laboratory investigations under conditions that mimic Titan’s troposphere providing a detailed picture of the cloud layers. A solid methane cloud with a nitrogen content of less than 14% and a liquid methane-nitrogen cloud with a nitrogen content of ∼30% form above ∼19 km and below ∼16 km altitude, respectively. Contrary to previous assertions, long-lived supercooled liquid methane-nitrogen droplets can be sustained in the region in between. The results demonstrate that a cloud gap could only form in the presence of high amounts of other traces species (ethane nuclei, tholin particles, etc.).  相似文献   

6.
Methane is, together with N2, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C2H2 (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH3, CH2 and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry at 248 nm by comparing the chemical evolution observed after irradiation of CH4 at 248 and at 121.6 nm (Ly-α). It is indeed important to see if the chemistry is driven the same way at both wavelengths in particular because, on Titan, methane photolysis mainly involves Ly-α photons. An approach combining experiments and theoretical analysis by means of a specifically adapted 0-D model has thus been developed and is presented in this paper. The results obtained clearly indicate that the chemistry is different depending on the wavelength. They also suggest that at 248 nm, methane dissociation is in competition with ionisation, which could occur through a three-photon absorption process. As a consequence, 248 nm photolysis appears to be unsuitable to study methane neutral photochemistry alone. The implications of this result on our laboratory simulation program and new experimental developments are discussed. Additional information on methane photochemistry at 121.6 nm are also obtained.  相似文献   

7.
Recent observations have evidenced traces of methane (CH4) heterogeneously distributed in the martian atmosphere. However, because the lifetime of CH4 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 CH4. 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 the 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 dioxide, 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 CH4-rich atmosphere has existed or if a subsurface source of CH4 has been (or is still) present.  相似文献   

8.
Using spectra taken with NIRSPEC (Near Infrared Spectrometer) and adaptive optics on the Keck II telescope, we resolved the latitudinal variation of the 3ν2 band of CH3D at 1.56 μm. As CH3D is less abundant than CH4 by a factor of 50±10×10-5, these CH3D lines do not saturate in Titan’s atmosphere, and are well characterized by laboratory measurements. Thus they do not suffer from the large uncertainties of the CH4 lines that are weak enough to be unsaturated in Titan. Our measurements of the methane abundance are confined to the latitude range of 32°S-18°N and longitudes sampled by a 0.04″ slit centered at ∼195°W. The methane abundance below 10 km is constant to within 20% in the tropical atmosphere sampled by our observations, consistent with the low surface insolation and lack of surface methane [Griffith, C.A., McKay, C.P., Ferri, F., 2008. Astrophys. J. 687, L41-L44].  相似文献   

9.
We propose an interpretation of the composition of volatiles observed in comets based on their trapping in the form of clathrate hydrates in the solar nebula. The formation of clathrates is calculated from the statistical thermodynamics of Lunine and Stevenson (1985, Astrophys. J. Suppl. 58, 493-531), and occurs in an evolutionary turbulent solar nebula described by the model of Hersant et al. (2001, Astrophys. J. 554, 391-407). It is assumed that clathrate hydrates were incorporated into the icy grains that formed cometesimals. The strong depletion of the N2 molecule with respect to CO observed in some comets is explained by the fact that CO forms clathrate hydrates much more easily than does N2. The efficiency of this depletion, as well as the amount of trapped CO, depends upon the amount of water ice available in the region where the clathration took place. This might explain the diversity of CO abundances observed in comets. The same theory, applied to the trapping of volatiles around 5 AU, explains the enrichments in Ar, Kr, Xe, C, and N with respect to the solar abundance measured in the deep troposphere of Jupiter [Gautier et al 2001a] and [Gautier et al 2001b].  相似文献   

10.
Methane clathrate hydrate reservoirs capped by overlying permafrost have been proposed as potential sources of atmospheric methane plumes on Mars. However, the surface flux of methane from hydrate dissociation is limited by the diffusion rate of methane through the overlying ice. Assuming hydrates underlay the entire plume footprint, the maximum diffusion path length is expected to be less than 15 m, depths too shallow to stabilize pure methane hydrates under Mars geothermal and lithostatic conditions at low to mid latitudes. Therefore, pure methane hydrates confined within permafrost could not produce methane surface fluxes of the magnitude observed near the equator. However, the addition of 10% H2S, a secondary gas commonly associated with methane production on Earth, expands the hydrate stability field, with clathrates expected within 10 m of the surface at the equator and at depths less than 1 m at higher latitudes. This indicates that H2S would also be expected to be released as well as methane if the plumes have a confined hydrate reservoir source.  相似文献   

11.
We discuss in this paper possible roles of methane and carbon dioxide in geological processes on Mars. These volatiles in the martian crust may migrate upward from their sources either directly or via various traps (structural, sedimentary, ground ice, gas hydrates). They are then likely emitted to the atmosphere by seepage or through diverse vent structures. Though gas hydrates have never been directly detected on Mars, theoretical studies favor their presence in the crust and polar caps; they could have played an important role as significant gas reservoirs in the subsurface. The martian gas hydrates would possibly be a binary system of methane and carbon dioxide occupying clathrate cavities. Landforms such as mud volcanoes with well-known linkage to gas venting are extensively distributed on Earth, and methane is the primary gas involved. Thus, identification of these landforms on Mars could suggest that methane and possibly carbon dioxide have contributed to geological processes of the planet. For example, we present a newly identified field in Chryse Planitia where features closely resembling terrestrial mud volcanoes occur widely, though with no observable activity. We also present results of a preliminary search for possible recent or present-day, methane-emission zones in the regions over which enrichments of atmospheric methane have been reported.  相似文献   

12.
There have been several reports of methane on Mars at the 10-60 ppbv level. Most suggest that methane is both seasonally and latitudinally variable. Here we review why variable methane on Mars is physically and chemically implausible, and then we critically review the published reports. There is no known mechanism for destroying methane chemically on Mars. But if there is one, methane oxidation would deplete the O2 in Mars’s atmosphere in less than 10,000 years unless balanced by an equally large unknown source of oxidizing power. Physical sequestration does not raise these questions, but adsorption in the regolith or condensation in clathrates ignore competition for adsorption sites or are inconsistent with clathrate stability, respectively. Furthermore, any mechanism that relies on methane’s van der Waals’ attraction is inconsistent with the continued presence of Xe in the atmosphere at the 60 ppbv level. We then use the HITRAN database and transmission calculations to identify and characterize the absorption lines that would be present on Earth or Mars at the wavelengths of the published observations. These reveal strong competing telluric absorption that is most problematic at just those wavelengths where methane’s signature seems most clearly seen from Earth. The competing telluric lines must be removed with models. The best case for martian methane was made for the 12CH4ν3 R0 and R1 lines seen in blueshift when Mars was approaching Earth in early 2003 (Mumma, M.J., Villanueva, G.L., Novak, R.E., Hewagama, T., Bonev, B.P., DiSanti, M.A., Mandell, A.M., Smith, M.D. [2009]. Science 323, 1041-1045). For these the Doppler shift moves the two martian lines into near coincidence with telluric 13CH4ν3 R1 and R2 lines that are 10-50× stronger than the inferred martian lines. By contrast, the 12CH4ν3 R0 and R1 lines when observed in redshift do not contend with telluric 13CH4. For these lines, Mumma et al.’s observations and analyses are consistent with an upper limit on the order of 3 ppbv.  相似文献   

13.
We analyze observations taken with Cassini’s Visual and Infrared Mapping Spectrometer (VIMS), to determine the current methane and haze latitudinal distribution between 60°S and 40°N. The methane variation was measured primarily from its absorption band at 0.61 μm, which is optically thin enough to be sensitive to the methane abundance at 20-50 km altitude. Haze characteristics were determined from Titan’s 0.4-1.6 μm spectra, which sample Titan’s atmosphere from the surface to 200 km altitude. Radiative transfer models based on the haze properties and methane absorption profiles at the Huygens site reproduced the observed VIMS spectra and allowed us to retrieve latitude variations in the methane abundance and haze. We find the haze variations can be reproduced by varying only the density and single scattering albedo above 80 km altitude. There is an ambiguity between methane abundance and haze optical depth, because higher haze optical depth causes shallower methane bands; thus a family of solutions is allowed by the data. We find that haze variations alone, with a constant methane abundance, can reproduce the spatial variation in the methane bands if the haze density increases by 60% between 20°S and 10°S (roughly the sub-solar latitude) and single scattering absorption increases by 20% between 60°S and 40°N. On the other hand, a higher abundance of methane between 20 and 50 km in the summer hemisphere, as much as two times that of the winter hemisphere, is also possible, if the haze variations are minimized. The range of possible methane variations between 27°S and 19°N is consistent with condensation as a result of temperature variations of 0-1.5 K at 20-30 km. Our analysis indicates that the latitudinal variations in Titan’s visible to near-IR albedo, the north/south asymmetry (NSA), result primarily from variations in the thickness of the darker haze layer, detected by Huygens DISR, above 80 km altitude. If we assume little to no latitudinal methane variations we can reproduce the NSA wavelength signatures with the derived haze characteristics. We calculate the solar heating rate as a function of latitude and derive variations of ∼10-15% near the sub-solar latitude resulting from the NSA. Most of the latitudinal variations in the heating rate stem from changes in solar zenith angle rather than compositional variations.  相似文献   

14.
This work presents the first study of the gaseous products resulting from the partial dissociation of methane and nitrogen in the PAMPRE experimental setup simulating Titan’s atmospheric chemistry.Using cryogenic trapping, the gaseous products generated from the chemical reactions occurring in the reactor have been trapped. Analyses of these products by gas chromatography coupled to mass spectrometry have allowed the detection and identification of more than 30 reaction products. Most of them are identified as nitrile species, accompanied by aliphatic hydrocarbons and a few aromatics compounds. The observed species are in agreement with the data from the recent Cassini-Huygens mission as well as from other laboratory setups capable of dissociating nitrogen and methane. This work emphasizes the probable importance of nitrogen-bearing compounds in the chemistry taking place in Titan’s atmosphere.Furthermore, a quantification of mono-nitriles with saturated alkyl chains has been performed relatively to hydrogen cyanide and shows a power law dependence in their concentration. This dependence is consistent with the Cassini-INMS data and Titan’s photochemical models.An empirical relationship has been extracted from our experimental data: [CxH2x−1N] = 100x−5, where x is the number of carbon atoms in the nitrile molecule. This relationship can be directly used in order to foretell the concentration of heavier nitriles induced by chemistry in Titan’s atmosphere.  相似文献   

15.
Chemical reactions and volatile supply through hypervelocity impacts may have played a key role for the origin and evolution of both planetary and satellite atmospheres. In this study, we evaluate the role of impact-induced N2 production from reduced nitrogen-bearing solids proposed to be contained in Titan’s crust, ammonium sulfate ((NH4)2SO4), for the replenishment of N2 to the atmosphere in Titan’s history. To investigate the conversion of (NH4)2SO4 into N2 by hypervelocity impacts, we measured gases released from (NH4)2SO4 that was exposed to hypervelocity impacts created by a laser gun. The sensitivity and accuracy of the measurements were enhanced by using an isotope labeling technique for the target. We obtained the efficiency of N2 production from (NH4)2SO4 as a function of peak shock pressure ranging from ∼8 to ∼45 GPa. Our results indicate that the initial and complete shock pressures for N2 degassing from (NH4)2SO4 are ∼10 and ∼25 GPa, respectively. These results suggest that cometary impacts on Titan (i.e., impact velocity vi > ∼8 km/s) produce N2 efficiently; whereas satellitesimal impacts during the accretion (i.e., vi < 4 km/s) produce N2 only inefficiently. Even when using the proposed small amount of (NH4)2SO4 content in the crust (∼4 wt.%) (Fortes, A.D. et al., 2007. Icarus 188, 139-153), the total amount of N2 provided through cometary impacts over 4.5 Ga reaches ∼2-6 times the present atmospheric N2 (i.e., ∼7 × 1020-2 × 1021 [mol]) based on the measured production efficiency and results of a hydrodynamic simulation of cometary impacts onto Titan. This implies that cometary impacts onto Titan’s crust have the potential to account for a large part of the present N2 through the atmospheric replenishment after the accretion.  相似文献   

16.
《Planetary and Space Science》2007,55(10):1246-1256
Small amounts of methane have been detected in the atmosphere of Mars, though the actual sources of the gas remain unknown. Thermodynamic conditions on Mars suggest that gas clathrate hydrate deposits might exist at the polar caps and in some areas of the planetary subsurface. We review the literature available on the detection of methane in the martian atmosphere and the presence of gas clathrate hydrates on Mars. The possibility of martian methane clathrate deposits is established, and initial sources for the sequestered methane are discussed. Based on correlated data and information from disparate sources, we conclude that subsurface methane clathrate deposits are a possible immediate source for the observed atmospheric methane on Mars.  相似文献   

17.
An investigation of the capabilities and science goals of a submillimeter-wave heterodyne sounder onboard a Titan orbiter is presented. Based on a model of Titan’s submillimeter spectrum, and including realistic instrumental performances, we show that passive limb observations of Titan’s submillimeter radiation would bring novel and unique information on the dynamical and chemical state of Titan’s atmosphere, particularly in the so far poorly probed 500-900 km region. The 300-360, 540-660 and 1080-1280 GHz spectral ranges appear especially promising, and could be explored with an instrument equipped with a tunable local oscillator system. Vertical temperature profiles can be determined up to ∼1200 km using rotational lines of CH4, CO, and HCN. Winds can be measured over the 200-1200 km altitude range with an accuracy of 3-5 m/s from Doppler shift measurements of any strong optically thin line. Numerous molecular species are accessible, including H2O, NH3, CH3C2H, CH2NH, and several nitriles (HC3N, HC5N, CH3CN, and C2H3CN). Many of them are expected to be detectable in a large fraction of the atmosphere and in some cases at all levels, providing an observational link between stratospheric and thermospheric chemistry. Isotopic variants of some of these species can also be measured, providing new measurements of H, C, N, and O isotopic ratios. Mapping of the thermal, wind, and composition fields, best achieved from a polar orbit and with an articulated antenna, would provide a new view of the couplings between chemistry and dynamics over an extended altitude range of Titan’s atmosphere. Additional science goals at Saturn and Enceladus are briefly discussed.  相似文献   

18.
19.
In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH4/N2 atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H2, HCN, C2N2, C2H2, C2H4, C2H6, NH3 and H2CN. The annual production of these compounds was estimated in the Titan’s atmosphere.  相似文献   

20.
The appearance of convective clouds in Titan’s troposphere has been documented from ground-based observation for more than a decade. Cloud tops have been reported between 14 and 25 km. Higher resolution Cassini data have shown smaller portions of the cloud system can reach up to 42 km. We use the Titan Regional Atmospheric Modeling System (TRAMS) to explore environments which allow convective clouds to reach the tropopause. In general, cloud tops remain below 30 km, but for environments where the surface humidity of methane is greater than 50%, a small portion at the center of the cloud rises briefly to higher altitudes; for ?65% humidity, the cloud top reaches nearly to the tropopause (∼40 km). A number of other parameters also have noticeable affects on cloud top such as nucleation critical saturation, haze abundance, and collisional growth of cloud particles.  相似文献   

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