Ammonium sulfate on Titan: Possible origin and role in cryovolcanism

We model the chemical evolution of Titan, wherein primordial NH₃ reacts with sulfate-rich brines leached from the silicate core during its hydration. The resulting differentiated body consists of a serpentinite core overlain by a high-pressure ice VI mantle, a liquid layer of aqueous ammonium sulfate, and a heterogeneous shell of methane clathrate, low-pressure ice Ih and solid ammonium sulfate. Cooling of the subsurface ocean results in underplating of the outer shell with ice Ih; this gravitationally unstable system can produce compositional plumes as ice Ih ascends buoyantly. Ice plumes may aid in advection of melt pockets through the shell and, in combination with surface topography, provide the necessary hydraulic pressure gradients to drive such melts to the surface. Moreover, contact between the magma and wall rock (methane clathrate) will allow some methane to dissolve in the magma, as well as eroding fragments of wall rock that can be transported as xenoliths. Upon rising to the clathrate decomposition depth (∼2 MPa, or 1700 m), the entrained xenoliths will break down to ice + methane gas, powering highly explosive eruptions with lava fountains up to several kilometers high. Hence we predict that Titan is being resurfaced by cryoclastic ash consisting of ice and ammonium sulfate (or its tetrahydrate), providing an abundance of sedimentary grains, a potential source of bedload for fluvial transport and erosion, and of sand-sized material for aeolian transport and dune-building. The infrared reflectance spectrum of ammonium sulfate makes it a plausible candidate for the 5 μm-bright material on Titan's surface.     

Titan’s internal structure and the evolutionary consequences

Titan’s moment of inertia (MoI), estimated from the quadrupole gravity field measured by the Cassini spacecraft, is 0.342, which has been interpreted as evidence of a partially differentiated internal mass distribution. It is shown here that the observed MoI is equally consistent with a fully differentiated internal structure comprising a shell of water ice overlying a low-density silicate core; depending on the chemistry of Titan’s subsurface ocean, the core radius is between 1980 and 2120 km, and its uncompressed density is 2570–2460 kg m^?3, suggestive of a hydrated CI carbonaceous chondrite mineralogy. Both the partially differentiated and fully differentiated hydrated core models constrain the deep interior to be several hundred degrees cooler than previously thought. I propose that Titan has a warm wet core below, or buffered at, the high-pressure dehydration temperature of its hydrous constituents, and that many of the gases evolved by thermochemical and radiogenic processes in the core (such as CH₄ and ⁴⁰Ar, respectively) diffuse into the icy mantle to form clathrate hydrates, which in turn may provide a comparatively impermeable barrier to further diffusion. Hence we should not necessarily expect to see a strong isotopic signature of serpentinization in Titan’s atmosphere.     

The D/H Ratio in Methane in Titan: Origin and History

We propose a new interpretation of the D/H ratio in CH₄ observed in the atmosphere of Titan. Using a turbulent evolutionary model of the subnebula of Saturn (O. Mousis et al. 2002, Icarus156, 162-175), we show that in contrast to the current scenario, the deuterium enrichment with respect to the solar value observed in Titan cannot have occurred in the subnebula. Instead, we argue that values of the D/H ratio measured in Titan were obtained in the cooling solar nebula by isotopic thermal exchange of hydrogen with CH₃D originating from interstellar methane D-enriched ices that vaporized in the nebula. The rate of the isotopic exchange decreased with temperature and became fully inhibited around 200 K. Methane was subsequently trapped in crystalline ices around 10 AU in the form of clathrate hydrates formed at 60 K, and incorporated into planetesimals that formed the core of Titan. The nitrogen-methane atmosphere was subsequently outgassed from the decomposition of the hydrates (Mousis et al. 2002). By use of a turbulent evolutionary model of the solar nebula (O. Mousis et al. 2000, Icarus148, 513-525), we have reconstructed the entire story of D/H in CH₄, from its high value in the early solar nebula (acquired in the presolar cloud) down to the value measured in Titan's atmosphere today. Considering the two last determinations of the D/H ratio in Titan—D/H=(7.75±2.25)×10⁻⁵ obtained from ground-based observations (Orton 1992, In: Symposium on Titan, ESA SP-338, pp. 81-85), and D/H=(8.75^+3.25_−2.25)×10⁻⁵, obtained from ISO observations (Coustenis et al. 2002, submitted for publication)—we inferred an upper limit of the D/H ratio in methane in the early outer solar nebula of about 3×10⁻⁴. Our approach is consistent with the scenario advocated by several authors in which the atmospheric methane of Titan is continuously replenished from a reservoir of clathrate hydrates of CH₄ at high pressures, located in the interior of Titan. If this scenario is correct, observations of the satellite to be performed by the radar, the imaging system, and other remote sensing instruments aboard the spacecraft of the Cassini-Huygens mission from 2004 to 2008 should reveal local disruptions of the surface and other signatures of the predicted outgassing.     

Phase separation in giant planets: inhomogeneous evolution of Saturn

We present the first models of Jupiter and Saturn to couple their evolution to both a radiative-atmosphere grid and to high-pressure phase diagrams of hydrogen with helium and other admixtures. We find that prior calculated phase diagrams in which Saturn's interior reaches a region of predicted helium immiscibility do not allow enough energy release to prolong Saturn's cooling to its known age and effective temperature. We explore modifications to published phase diagrams that would lead to greater energy release, and propose a modified H-He phase diagram that is physically reasonable, leads to the correct extension of Saturn's cooling, and predicts an atmospheric helium mass fraction Y_atmos=0.185, in agreement with recent estimates. We also explore the possibility of internal separation of elements heavier than helium, and find that, alternatively, such separation could prolong Saturn's cooling to its known age and effective temperature under a realistic phase diagram and heavy element abundance (in which case Saturn's Y_atmos would be solar but heavier elements would be depleted). In none of these scenarios does Jupiter's interior evolve to any region of helium or heavy-element immiscibility: Jupiter evolves homogeneously to the present day. We discuss the implications of our calculations for Saturn's primordial core mass.     

Titan's methane cycle

Methane is key to sustaining Titan's thick nitrogen atmosphere. However, methane is destroyed and converted to heavier hydrocarbons irreversibly on a relatively short timescale of approximately 10-100 million years. Without the warming provided by CH₄-generated hydrocarbon hazes in the stratosphere and the pressure induced opacity in the infrared, particularly by CH₄-N₂ and H₂-N₂ collisions in the troposphere, the atmosphere could be gradually reduced to as low as tens of millibar pressure. An understanding of the source-sink cycle of methane is thus crucial to the evolutionary history of Titan and its atmosphere. In this paper we propose that a complex photochemical-meteorological-hydrogeochemical cycle of methane operates on Titan. We further suggest that although photochemistry leads to the loss of methane from the atmosphere, conversion to a global ocean of ethane is unlikely. The behavior of methane in the troposphere and the surface, as measured by the Cassini-Huygens gas chromatograph mass spectrometer, together with evidence of cryovolcanism reported by the Cassini visual and infrared mapping spectrometer, represents a “methalogical” cycle on Titan, somewhat akin to the hydrological cycle on Earth. In the absence of net loss to the interior, it would represent a closed cycle. However, a source is still needed to replenish the methane lost to photolysis. A hydrogeochemical source deep in the interior of Titan holds promise. It is well known that in serpentinization, hydration of ultramafic silicates in terrestrial oceans produces H_2(aq), whose reaction with carbon grains or carbon dioxide in the crustal pores produces methane gas. Appropriate geological, thermal, and pressure conditions could have existed in and below Titan's purported water-ammonia ocean for “low-temperature” serpentinization to occur in Titan's accretionary heating phase. On the other hand, impacts could trigger the process at high temperatures. In either instance, storage of methane as a stable clathrate-hydrate in Titan's interior for later release to the atmosphere is quite plausible. There is also some likelihood that the production of methane on Titan by serpentinization is a gradual and continuous on-going process.     

Stability of methane clathrate hydrates under pressure: Influence on outgassing processes of methane on Titan

We have conducted high-pressure experiments in the H₂O-CH₄ and H₂O-CH₄-NH₃ systems in order to investigate the stability of methane clathrate hydrates, with an optical sapphire-anvil cell coupled to a Raman spectrometer for sample characterization. The results obtained confirm that three factors determine the stability of methane clathrate hydrates: (1) the bulk methane content of the samples; (2) the presence of additional gas compounds such as nitrogen; (3) the concentration of ammonia in the aqueous solution. We show that ammonia has a strong effect on the stability of methane clathrates. For example, a 10 wt.% NH₃ solution decreases the dissociation temperature of methane clathrates by 14-25 K at pressures above 5 MPa. Then, we apply these new results to Titan’s conditions. Dissociation of methane clathrate hydrates and subsequent outgassing can only occur in Titan’s icy crust, in presence of locally large amounts of ammonia and in a warm context. We propose a model of cryomagma chamber within the crust that provides the required conditions for methane outgassing: emplacement of an ice plume triggers the melting (if solid) or heating (if liquid) of large ammonia-water pockets trapped at shallow depth, and the generated cryomagmas dissociate surrounding methane clathrate hydrates. We show that this model may allow for the outgassing of significant amounts of methane, which would be sufficient to maintain the presence of methane in Titan’s atmosphere for several tens of thousands of years after a large cryovolcanic event.     

Evaluation of the possible presence of clathrate hydrates in Europa's icy shell or seafloor

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.     

The long-term stability of a possible aqueous ammonium sulfate ocean inside Titan

We model the thermal evolution of a subsurface ocean of aqueous ammonium sulfate inside Titan using a parameterized convection scheme. The cooling and crystallization of such an ocean depends on its heat flux balance, and is governed by the pressure-dependent melting temperatures at the top and bottom of the ocean. Using recent observations and previous experimental data, we present a nominal model which predicts the thickness of the ocean throughout the evolution of Titan; after 4.5 Ga we expect an aqueous ammonium sulfate ocean 56 km thick, overlain by a thick (176 km) heterogeneous crust of methane clathrate, ice I and ammonium sulfate. Underplating of the crust by ice I will give rise to compositional diapirs that are capable of rising through the crust and providing a mechanism for cryovolcanism at the surface. We have conducted a parameter space survey to account for possible variations in the nominal model, and find that for a wide range of plausible conditions, an ocean of aqueous ammonium sulfate can survive to the present day, which is consistent with the recent observations of Titan's spin state from Cassini radar data [Lorenz, R.D., Stiles, B.W., Kirk, R.L., Allison, M.D., del Marmo, P.P., Iess, L., Lunine, J.I., Ostro, S.J., Hensley, S., 2008. Science 319, 1649-1651].     

Reduced sulfur–carbon–water systems on Mars may yield shallow methane hydrate reservoirs

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.     

The effect of gravitational and pressure torques on Titan's length-of-day variations

Cassini radar observations show that Titan's spin is slightly faster than synchronous spin. Angular momentum exchange between Titan's surface and the atmosphere over seasonal time scales corresponding to Saturn's orbital period of 29.5 year is the most likely cause of the observed non-synchronous rotation. We study the effect of Saturn's gravitational torque and torques between internal layers on the length-of-day (LOD) variations driven by the atmosphere. Because static tides deform Titan into an ellipsoid with the long axis approximately in the direction to Saturn, non-zero gravitational and pressure torques exist that can change the rotation rate of Titan. For the torque calculation, we estimate the flattening of Titan and its interior layers under the assumption of hydrostatic equilibrium. The gravitational forcing by Saturn, due to misalignment of the long axis of Titan with the line joining the mass centers of Titan and Saturn, reduces the LOD variations with respect to those for a spherical Titan by an order of magnitude. Internal gravitational and pressure coupling between the ice shell and the interior beneath a putative ocean tends to reduce any differential rotation between shell and interior and reduces further the LOD variations by a few times. For the current estimate of the atmospheric torque, we obtain LOD variations of a hydrostatic Titan that are more than 100 times smaller than the observations indicate when Titan has no ocean as well as when a subsurface ocean exists. Moreover, Saturn's torque causes the rotation to be slower than synchronous in contrast to the Cassini observations. The calculated LOD variations could be increased if the atmospheric torque is larger than predicted and or if fast viscous relaxation of the ice shell could reduce the gravitational coupling, but it remains to be studied if a two order of magnitude increase is possible and if these effects can explain the phase difference of the predicted rotation variations. Alternatively, the large differences with the observations may suggest that non-hydrostatic effects in Titan are important. In particular, we show that the amplitude and phase of the calculated rotation variations are similar to the observed values if non-hydrostatic effects could strongly reduce the equatorial flattening of the ice shell above an internal ocean.     

Metastable methane clathrate particles as a source of methane to the martian atmosphere

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.     

The role of photochemical processes in evolution of the isotopic composition of the atmosphere of Titan

Molecular nitrogen, the main component of the modern atmosphere of Titan, may have formed without significant changes in the nitrogen and hydrogen isotopic composition from the clathrate hydrate of ammonia NH₃ · H₂O_SLD, which is the main accreted form of nitrogen. The most preferable transformation mechanism of NH₃ · H₂O_SLD into atmospheric N₂ is its thermal decomposition in the interior of Titan rather than the photochemical decomposition of ammonia in the upper atmosphere of early Titan. The photolysis of ammonia does not lead to a change in the isotopic composition of nitrogen, as all the nitrogen remains in Titan’s atmosphere. The photolysis of NH does not lead to a change in the isotopic composition of nitrogen in Titan’s atmosphere. Fractionation of hydrogen and nitrogen isotopes during the impacts of comets with Titan does not seem to be significant either. It will be possible to determine the dissociative fractionation factor, the original ratio ¹⁴N/¹⁵N, and the mass of Titan’s original atmosphere when fractionation of nitrogen isotopes in Titan’s atmosphere is examined in additional theoretical and experimental studies that take into account processes occurring during the formation of a system of Saturn’s satellites.     

Titan's damp ground: Constraints on Titan surface thermal properties from the temperature evolution of the Huygens GCMS inlet

Abstract— A simple thermal model is developed to determine the temperature history of the inlet tube of the Huygens probe gas chromatograph mass spectrometer (GCMS) after its fortuitous emplacement on the surface of Saturn's moon Titan. The model parameters are adjusted to match the recorded temperature history of a nearby heater, taking into account heat losses by conduction to the rest of the probe and to Titan's cold atmosphere. The model suggests that after impact when forced convective cooling ceased, the inlet temperature rose from ?110 K to an asymptotic value of only ?145 K. This requires that the inlet was embedded in a surface that acted as an effective heat sink, most plausibly interpreted as wet or damp with liquid methane. The data appear inconsistent with a tar or dry, fine‐grained surface, and the inlet was not warm enough to devolatilize methane hydrate.     

The phase diagram of water and the magnetic fields of Uranus and Neptune

The interior of giant planets can give valuable information on formation and evolution processes of planetary systems. However, the interior and evolution of Uranus and Neptune is still largely unknown. In this paper, we compare water-rich three-layer structure models of these planets with predictions of shell structures derived from magnetic field models. Uranus and Neptune have unusual non-dipolar magnetic fields contrary to that of the Earth. Extensive three-dimensional simulations of Stanley and Bloxham (Stanley, S., Bloxham, J. [2004]. Nature 428, 151-153) have indicated that such a magnetic field is generated in a rather thin shell of at most 0.3 planetary radii located below the H/He rich outer envelope and a conducting core that is fluid but stably stratified. Interior models rely on equation of state data for the planetary materials which have usually considerable uncertainties in the high-pressure domain. We present interior models for Uranus and Neptune that are based on ab initio equation of state data for hydrogen, helium, and water as the representative of all heavier elements or ices. Based on a detailed high-pressure phase diagram of water we can specify the region where superionic water should occur in the inner envelope. This superionic region correlates well with the location of the stably-stratified region as found in the dynamo models. Hence we suggest a significant impact of the phase diagram of water on the generation of the magnetic fields in Uranus and Neptune.     

Spectral reflectivities of the Galilean satellites and Titan, 0.32 to 0.86 micrometers

A spectrophotometric observational study of the Galilean satellites and Titan was carried out at 0.004-μm (40-Å) resolution over the spectral range 0.32 to 0.86 μm. A standard lunar area was used as a primary spectroscopic standard to establish the relative reflection spectra of the objects by ratioing the sky-corrected satellite spectra to the standard area on the Moon. J1 (Io) is found to have a spectral edge at 0.33 μm that has not been previously reported. The increase in reflectivity from 0.4 to 0.5 μm and the band at 0.56 μm are confirmed. A weak band at 0.56 μm is probable on J2 (Europa) and possible on J3 (Ganymede). J4 (Callisto) shows no spectral features that have not been previously reported. On Titan, no temporal variations in the methane bands greater than 2% were found, indicating that the effective path length in the Titan atmosphere did not change over the 3-month period of this study. A new absorption band of methane at 0.68 μm was found on Titan. We propose an extension of the evaporite model of Fanale et al. (1974, 1977) and the sulfur mixing models of Wamsteker et al. (1974) in which the primary constituent of the surface of J1 is elemental sulfur sublimated onto the surface by photodissociation of hydrogen sulfide outgassing from the interior. The sulfur is continually renewed by sublimation, sputtering, and redeposition. At low temperatures irradiation produces stable S₂, S₃, S₄, S₆, and long chain polymers. Some of these allotropes have an edge at 0.33 μm, a rising reflectance between 0.4 and 0.5 μm a band at 0.56 μm. All of these features are found in the spectrum of J1. We conclude that the lunar ratioing technique used in this study is well suited for determining the relative reflection spectra of solar system objects.     

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.     

Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere

New low-temperature methane absorption coefficients pertinent to the Titan environment are presented as derived from the Huygens DISR spectral measurements combined with the in-situ measurements of the methane gas abundance profile measured by the Huygens Gas Chromatograph/Mass Spectrometer (GCMS). The visible and near-infrared spectrometers of the descent imager/spectral radiometer (DISR) instrument on the Huygens probe looked upward and downward covering wavelengths from 480 to 1620 nm at altitudes from 150 km to the surface during the descent to Titan's surface. The measurements at continuum wavelengths were used to determine the vertical distribution, single-scattering albedos, and phase functions of the aerosols. The gas chromatograph/mass spectrometer (GCMS) instrument on the probe measured the methane mixing ratio throughout the descent. The DISR measurements are the first direct measurements of the absorbing properties of methane gas made in the atmosphere of Titan at the pathlengths, pressures, and temperatures that occur there. Here we use the DISR spectral measurements to determine the relative methane absorptions at different wavelengths along the path from the probe to the sun throughout the descent. These transmissions as functions of methane path length are fit by exponential sums and used in a haze radiative transfer model to compare the results to the spectra measured by DISR. We also compare the recent laboratory measurements of methane absorption at low temperatures [Irwin et al., 2006. Improved near-infrared methane band models and k-distribution parameters from 2000 to 9500 cm⁻¹ and implications for interpretation of outer planet spectra. Icarus 181, 309-319] with the DISR measurements. We find that the strong bands formed at low pressures on Titan act as if they have roughly half the absorption predicted by the laboratory measurements, while the weak absorption regions absorb considerably more than suggested by some extrapolations of warm measurements to the cold Titan temperatures. We give factors as a function of wavelength that can be used with the published methane coefficients between 830 and 1620 nm to give agreement with the DISR measurements. We also give exponential sum coefficients for methane absorptions that fit the DISR observations. We find the DISR observations of the weaker methane bands shortward of 830 nm agree with the methane coefficients given by Karkoschka [1994. Spectrophotometry of the jovian planets and Titan at 300- to 1000-nm wavelength: the methane spectrum. Icarus 111, 174-192]. Finally, we discuss the implications of our results for computations of methane absorption in the atmospheres of the outer planets.     

Kinetics of methane clathrate formation and dissociation under Mars relevant conditions

Spectral observations have detected methane within the martian atmosphere (Formisano, V., Atreya, S., Encrenaz, T., Ignatiev, N., Giuranna, M. [2004]. Science 306, 1758–1761; Mumma, M.J. et al. [2009]. Science 323, 1041–1045), however, the origin of the methane has not been determined. Methane clathrate (also referred to as methane hydrate) has been suggested as a potential subsurface reservoir, storing and releasing biologic and/or abiogenic methane. In this study, rates of methane hydrate formation and dissociation were measured experimentally at 234–264 K and 1.4–4.7 MPa to test the clathrate reservoir hypothesis. Initial formation rates range from 4.3 × 10^?6 to 8.1 × 10^?5 mol m^?2 s^?1. Results show decreasing rates of formation over time in individual experiments, indicating initial rapid clathration, followed by diffusion-limited transport of methane into the ice through the previously formed hydrate. These experiments indicate increased pressure results in increased formation rates, likely the result of higher concentration gradients, enhancing the methane diffusion flux into the solid phase. Experiments conducted at elevated temperatures produced faster initial rates of formation, resulting from increased kinetic energy of methane molecules and/or thickening of the Quasi-Liquid Layer. Based on this temperature dependence, the activation energy for methane hydrate formation from ice was determined to be 35.9 kJ/mol. Hydrate dissociation experiments initiated by depressurization or warming at conditions between 222 K and 265 K and 0.1–2.0 MPa were conducted following each formation experiment, yielding methane hydrate dissociation rates from 3.01 × 10^?6 to 9.92 × 10^?5 mol m^?2 s^?1. While both hydrate dissociation and formation showed decreasing instantaneous rates over the course of each experiment, the transition between the initial rate of dissociation and the interpreted diffusion-limited period of continued dissociation was more abrupt than that observed in formation experiments, supporting an ice shielding effect. The initial concentration of methane in the solid phase had a significant effect on hydrate dissociation rates. Higher methane concentrations in the solid phase produce faster initial rates, likely due to increased concentration gradients, thus increasing the diffusion component of dissociation. Increased temperatures also produced faster dissociation rates, yielding an activation energy for dissociation of 32.7 kJ/mol. The rates determined within this study suggest that small near-surface methane hydrate reservoirs are a feasible source for recent methane plumes detected on Mars. Rates of methane release from gas hydrates also indicate that gas hydrate dissociation may have played a role in forming ancient chaos terrain and associated outflow channels.