The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state 13C NMR spectroscopy suggests approximately equal to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of approximately equal to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.     

Titan’s atmosphere: An optimal gas mixture for aerosol production?

Here we present the first quantitative study of the gas to solid particle conversion in a Radio Frequency dusty plasma experiment simulating the complex atmospheric reactivity on Titan.Analogs of Titan’s aerosols have been produced in different N₂-CH₄ gas mixtures. Using in situ mass spectrometry, it has been found that, by varying the initial methane concentration, aerosols could be produced in methane steady state concentrations similar to Titan’s atmospheric conditions. In our experiment, an initial ∼5% methane concentration is necessary to ensure a ∼1.5% methane steady state concentration in the plasma.The tholin mass production rate has been quantified as a function of the initial methane concentration. A maximum was found for a steady state CH₄ concentration in agreement with Titan’s atmospheric CH₄ concentrations. At this maximum, the tholin C/N ratio is about 1.45 and the carbon gas to solid conversion yield is about 35%.We have modeled the mass production rate by a parabolic function, highlighting two competitive chemical regimes controlling the tholin production efficiency: an efficient growth process which is proportional to the methane consumption, and an inhibiting process which opposes the growth process and dominates it for initial methane concentrations higher than ∼5%. To explain these two opposite effects, we propose two mechanisms: one involving HCN patterns in the tholins for the growth process, and one involving the increasing amount of atomic hydrogen in the plasma as well as the increase in aliphatic contributions in the tholins for the inhibiting process. This study highlights new routes for understanding the chemical growth of the organic aerosols in Titan’s atmosphere.     

Laboratory experiments of Titan tholin formed in cold plasma at various pressures: implications for nitrogen-containing polycyclic aromatic compounds in Titan haze

Titan, the largest satellite of Saturn, has a thick nitrogen/methane atmosphere with a thick global organic haze. A laboratory analogue of Titan's haze, called tholin, was formed in an inductively coupled plasma from nitrogen/methane=90/10 gas mixture at various pressures ranging from 13 to 2300 Pa. Chemical and optical properties of the resulting tholin depend on the deposition pressure in cold plasma. Structural analyses by IR and UV/VIS spectroscopy, microprobe laser desorption/ionization mass spectrometry, and Raman spectroscopy suggest that larger amounts of aromatic ring structures with larger cluster size are formed at lower pressures (13 and 26 Pa) than at higher pressures (160 and 2300 Pa). Nitrogen is more likely to incorporate into carbon networks in tholins formed at lower pressures, while nitrogen is bonded as terminal groups at higher pressures. Elemental analysis reveals that the carbon/nitrogen ratio in tholins increases from 1.5-2 at lower pressures to 3 at 2300 Pa. The increase in the aromatic compounds and the decrease in C/N ratio in tholin formed at low pressures indicate the presence of the nitrogen-containing polycyclic aromatic compounds in tholin formed at low pressures. Tholin formed at high pressure (2300 Pa) consists of a polymer-like branched chain structure terminated with CH₃, NH₂, and CN with few aromatic compounds. Reddish-brown tholin films formed at low pressures (13-26 Pa) shows stronger absorptions (almost 10 times larger k-value) in the UV/VIS range than the yellowish tholin films formed at high pressures (160 and 2300 Pa). The tholins formed at low pressures may be better representations of Titan's haze than those formed at high pressures, because the optical properties of tholin formed at low pressures agree well with that of Khare et al. (1984a, Icarus 60, 127-137), which have been shown to account for Titan's observed geometric albedo. Thus, the nitrogen-containing polycyclic aromatic compounds we find in tholin formed at low pressure may be present in Titan's haze. These aromatic compounds may have a significant influence on the thermal structure and complex organic chemistry in Titan's atmosphere, because they are efficient absorbers of UV radiation and efficient charge exchange intermediaries. Our results also indicate that the haze layers at various altitudes might have different chemical and optical properties.     

Composition of Titan''s surface from Cassini VIMS

Titan's bulk density along with Solar System formation models indicates considerable water as well as silicates as its major constituents. This satellite's dense atmosphere of nitrogen with methane is unique. Deposits or even oceans of organic compounds have been suggested to exist on Titan's solid surface due to UV-induced photochemistry in the atmosphere. Thus, the composition of the surface is a major piece of evidence needed to determine Titan's history. However, studies of the surface are hindered by the thick, absorbing, hazy and in some places cloudy atmosphere. Ground-based telescope investigations of the integral disk of Titan attempted to observe the surface albedo in spectral windows between methane absorptions by calculating and removing the haze effects. Their results were reported to be consistent with water ice on the surface that is contaminated with a small amount of dark material, perhaps organic material like tholin. We analyze here the recent Cassini Mission's visual and infrared mapping spectrometer (VIMS) observations that resolve regions on Titan. VIMS is able to see surface features and shows that there are spectral and therefore likely compositional units. By several methods, spectral albedo estimates within methane absorption windows between 0.75 and 5 μm were obtained for different surface units using VIMS image cubes from the Cassini-Huygens Titan T_a encounter. Of the spots studied, there appears to be two compositional classes present that are associated with the lower albedo and the higher albedo materials, with some variety among the brighter regions. These were compared with spectra of several different candidate materials. Our results show that the spectrum of water ice contaminated with a darker material matches the reflectance of the lower albedo Titan regions if the spectral slope from 2.71 to 2.79 μm in the poorly understood 2.8-μm methane window is ignored. The spectra for brighter regions are not matched by the spectrum of water ice or unoxidized tholin, in pure form or in mixtures with sufficient ice or tholin present to allow the water ice or tholin spectral features to be discerned. We find that the 2.8-μm methane absorption window is complex and seems to consist of two weak subwindows at 2.7 and 2.8 μm that have unknown opacities. A ratio image at these two wavelengths reveals an anomalous region on Titan that has a reflectance unlike any material so far identified, but it is unclear how much the reflectances in these two subwindows pertain to the surface.     

Optical constants of Titan tholins at mid-infrared wavelengths (2.5–25 μm) and the possible chemical nature of Titan’s haze particles

Complex organic materials may exist as haze layers in the atmosphere of Titan and as dark coloring agents on icy satellite surfaces. Laboratory measurements of optical constants of plausible complex organic materials are necessary for quantitative evaluation from remote sensing observations, and to document the existence of complex organic materials in the extraterrestrial environments. The recent Cassini VIMS and CIRS observations provide new constraints on Titan’s haze properties in the mid-infrared wavelength region. Here, we present the optical constants (2.5–25 μm) of Titan tholins generated with cold plasma irradiation of a N₂/CH₄ (90/10) gas mixture at pressures of 0.26 mbar, 1.6 mbar, and 23 mbar. Our new optical constants of three types of Titan tholins suggest that no single Titan tholin in this study fulfills all the observational constraints of the Titan haze material. The discrepancy remains a challenge for future modeling and laboratory efforts that aim toward a better understanding of Titan’s haze material.     

Evidence from scanning electron microscopy ofexperimental influences on the morphology of Triton andTitan tholins

To simulate experimentally the production of aerosols in the atmospheres of Titan andTriton, we have studied organic material (tholins) obtained by inductively coupled plasma fromCH₄ : N₂ gas mixtures, with ratios 10 : 90 for Titan simulations and 0.1 : 99.9 for Tritonsimulations. Observation of tholins by high performance scanning electron microscopy showsthat tholin morphology varies with the chemical composition of the initial gas mixture. Althoughthe role of the experimental design (especially the diameter of the discharge chamber) and theflux of matter were not fully investigated, it appears that they have a significant effect not on theoverall morphology of the tholins but on the size distribution of the particles.     

Analysis of the Time-Dependent Chemical Evolution of Titan Haze Tholin

Haze particles exert a significant influence over the thermodynamics and radiation absorption properties of the Titan haze, as well as its complex organic chemistry. Characterization of both the molecular and the submicrometer components of the haze is therefore vital for understanding the global properties of Titan. We have carried out a Titan tholin synthesis experiment and measured the time variation of the infrared spectrum of the product as a thin film developed. Also, to examine the possibility of oxygen contamination, we compared the infrared spectrum of the tholin film with that of a tholin film exposed to dry air and laboratory air. The objective of this study is to understand the chemical processes related to how simple organic molecules are processed into more complex haze particles. The progressive development of features characteristic of amines, aromatic and aliphatic hydrocarbons, and nitriles in the experimental mixture is clear. Of particular interest is the formation of aromatic rings after only a few seconds of glow discharge, indicating that these compounds appear to be intermediates between simple haze molecules and microphysical aerosols. The early dominance of aromatic ring structures is accompanied during the later stages of the experiment by the appearance of nitrile and amine compounds. This time-dependent succession of chemical structures provides vital clues to the possible chemical formation pathways of Titan haze aerosols.     

Estimated impact shock production of N2 and organic compounds on early Titan

Bombardment of Titan by Uranus-Neptune planetesimals and/or fragments of a disrupted Hyperion progenitor supplied more than enough energy to drive vigorous atmospheric shock chemistry. Chemical equilibrium modeling of the shock products in simulated atmospheres indicates that impact energy has produced large amounts of N₂ and organic compounds over Titan's history. The mole fraction of organic compounds in the shocked gas mixture (T = 1200−2500°K, P = 10⁻¹−10³bar) reaches a maximum of approximately 3% in a current Titan mixture and 12% in a primordial CH₄, NH₃-rich mixture. Atmospheric water mixing ratio controls the organic yield in shock reactions, but its limiting effect may have been reduced by cold-trapping of water in a cooling atmosphere. Kinetic inhibition of graphite formation in the shocked gas enhanced the yield of radicals and organic. The resulting mixture of carbonaceous soot and condensed hydrocarbons subsequently settled onto the surface; the depth of the generated layer was on the order of hundreds of meters. Impact shock energy was capable of converting massive amounts of NH₃ to N₂ early in Titan history—over twice the present atmospheric and 1.5 times the total ocean-atmospheric inventory of N₂. Shock conversion of NH₃ into N₂ bypasses the difficulties of other schemes of N₂ production and may have been of singular importance in Titan's atmospheric evolution.     

On the Possibility of Gly and Ala Amino Acids on Titan’s Surface

In view of the possible production of formaldehyde and acetaldehyde in Titan’s atmosphere, the production of α-amino nitriles, the precursors of Glycine and Alanine amino acids, is explored in the upper atmosphere of Titan. The presence of Glycine and Alanine amino acids or their precursor amino nitriles can be used as a diagnostic, respectively for the presence or absence of water locally on the surface of Titan.     

Optical constants of organic tholins produced in a simulated Titanian atmosphere: From soft x-ray to microwave frequencies

As part of a continuing series of experiments on the production of dark reddish organic solids, called tholins, by irradiation of cosmically abundant reducing gases, the synthesis from a simulated Titanian atmosphere of a tholin with a visible reflection spectrum similar to that of the high altitude aerosols responsible for the albedo and reddish color of Titan has been reported Sagan and Khare, 1981, Sagan and Khare, 1982, Orig. Life. 12, 280) and [C. Sagan, B. N. Khare, and J. Lewis, in press. In Saturn (M. S. Matthews and T. Gehrels, Eds.), Univ. of Arizona Press, Tucson]. The determination of the real (n) and imaginary (k) parts of the complex refractive index of thin films of such tholin prepared by continuous D.C. discharge through a 0.9 N₂/0.1 CH₄ gas mixture at 0.2 mb are reported. For $\text{250}\text{A}\text{?}\text{≤ γ ≤ 1000 μ}\text{m}\text{, n}\text{and}\text{k}$ have been determined from a combination of transmittance, specular reflectance, interferometric, Brewster angle, and ellipsometric polarization measurements; experimental uncertainties in n are estimated to be ±0.5, and in k ± 30%. Values of n(?1.65) and k (?0.004 to 0.08) in the visible range are consistent with deductions made by ground-based and spacecraft observations of Titan. Maximum values of k (?0.8) are near 1000 Å, and minimum values (?4 × 10^?4) are near 1.5 μm. Many infrared absorption features are present in k(γ), including the 4.6-μm nitrile band.     

Discharge experiments simulating chemical evolution on the surface of Titan

Saturn's moon Titan has been considered as one of the few places in our Solar System, where atmospheric and surface conditions could have produced organic compounds essential as precursors for an evolution of life. The Cassini-Huygens mission has provided new data on Titan's atmosphere and surface, which enabled us to simulate the chemical processes occurring under these conditions. Possible lightning events on Titan cannot only produce higher hydrocarbons, but also allow surface water ice to participate in the reaction scenario, resulting in CHO, CHN, and CHON compounds including several molecules relevant for the formation of amino acids and nucleic acids.     

Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds

Titan, Saturn's largest moon, has a thick nitrogen/methane atmosphere. The temperature and pressure conditions in Titan's atmosphere are such that the methane vapor should condense near the tropopause to form clouds. Several ground-based measurements have observed sparse cloud-like features in Titan's atmosphere, while the Cassini mission to Saturn has provided large scale images of the clouds. However, Titan's cloud formation conditions remain poorly constrained. Heterogeneous nucleation (from the vapor phase onto a solid or liquid aerosol surface) greatly enhances cloud formation relative to homogeneous nucleation. In order to elucidate the cloud formation mechanism near the tropopause, we have performed laboratory measurements of the adsorption of methane and ethane onto solid organic particles (tholins) representative of Titan's photochemical haze. We find that monolayers of methane adsorb onto tholin particles at saturation ratios less than unity. We also find that solid methane nucleates onto the adsorbed methane at a saturation ratio of S=1.07±0.008. This implies that Titan's methane clouds should form easily. This is consistent with recent measurements of the column of methane ruling out excessive methane supersaturation. In addition, we find ethane adsorbs onto tholin particles in a metastable phase prior to nucleation. However, ethane nucleation onto the adsorbed ethane occurs at a relatively high saturation ratio of S=1.36±0.08. These findings are consistent with the recent report of polar ethane clouds in Titan's lower stratosphere.     

Reflectance spectra of hydrated Titan tholins at cryogenic temperatures and implications for compositional interpretation of red objects in the outer Solar System

We report the visible and near-infrared (0.4-2.5 μm) laboratory bidirectional reflectance of hydrated Titan tholin at cryogenic temperatures (∼100-300 K). When compared with room temperature measurements, the visible and near-infrared color of hydrated Titan tholin becomes bluer by ∼14% at low temperatures in the 0.7-1.0 μm region. Assuming the observed color changes are representative of tholin-like materials we estimate the influence of such color changes on the interpretation of the Centaur Pholus and find that the modest color changes will not significantly alter existing interpretations.     

Experimental simulation of Titan's organic chemistry at low temperature

A wide range of experiments has already been carried out to simulate the chemical evolution of Titan. Such experiments can provide useful information on the possible nature of minor constituents, mostly organic, likely to be present in Titan's atmosphere. Indeed, all but one of the organic compounds already detected in Titan's atmosphere have been identified in simulation experiments. The exception, C4N2, as well as other compounds expected in Titan from theoretical modeling, such as other N-organics, mainly CH2N2, and polyynes, namely C6H2, have never been detected in experimental simulation. It turned out that these compounds were thermally unstable, and the temperature conditions used during the simulation experiments (including conditions used for chemical analysis) were not appropriate. We have recently started a new program of simulation experiments using temperature conditions close to those of Titan's environment, more compatible with the build-up and detection of organics only stable at low temperature. Spark discharge of N2-CH4 gas mixtures was carried out at low temperature in the range of 100-150 K. The analysis of the obtained products was performed through FTIR, GC and GC-MS techniques. GC-peak identification was done owing to its mass spectrum and, in most cases, by comparison of the retention time and of the mass spectrum with standards. We report here the first detection in Titan's simulation experiments of C6H2. Its abundance is a few 10(-2) relative to C4H2. We also report a tentative identification of HC5N (to be confirmed by use of standard) with an abundance of a few 10(-2) relative to HC3N. The possible presence of HC5N suggested by our work provides the occurrence of very novel pathways in the formation of Titan's organic aerosols, involving not only C and H but also N atoms.     

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.     

Prebiotic synthesis of adenine and amino acids under Europa-like conditions.

In order to simulate prebiotic synthetic processes on Europa and other ice-covered planets and satellites, we have investigated the prebiotic synthesis of organic compounds from dilute solutions of NH4CN frozen for 25 years at -20 and -78 degrees C. In addition, the aqueous products of spark discharge reactions from a reducing atmosphere were frozen for 5 years at -20 degrees C. We find that both adenine and guanine, as well as a simple set of amino acids dominated by glycine, are produced in substantial yields under these conditions. These results indicate that some of the key components necessary for the origin of life may have been available on Europa throughout its history and suggest that the circumstellar zone where life might arise may be wider than previously thought.     

Photochemistry of the atmosphere of Titan: comparison between model and observations

The photochemistry of simple molecules containing carbon, hydrogen, nitrogen, and oxygen atoms in the atmosphere of Titan has been investigated using updated chemical schemes and our own estimates of a number of key rate coefficients. Proper exospheric boundary conditions, vertical transport, and condensation processes at the tropopause have been incorporated into the model. It is argued that he composition, climatology, and evolution of Titan's atmosphere are controlled by five major processes: (a) photolysis and photosensitized dissociation of CH4; (b) conversion of H to H2 and escape of hydrogen; (c) synthesis of higher hydrocarbons; (d) coupling between nitrogen and hydrocarbons; (e) coupling between oxygen and hydrocarbons. Starting with N2, CH4, and H2O, and invoking interactions with ultraviolet sunlight, energetic electrons, and cosmic rays, the model satisfactorily accounts for the concentrations of minor species observed by the Voyager IRIS and UVS instruments. Photochemistry is responsible for converting the simpler atmospheric species into more complex organic compounds, which are subsequently condensed at the tropopause and deposited on the surface. Titan might have lost 5.6 x 10(4), 1.8 x 10(3), and 4.0 g cm-2, or the equivalent of 8, 0.25, and 5 x 10(-4) bars of CH4, N2, and CO, respectively, over geologic time. Implications of abiotic organic synthesis on Titan for the origin of life on Earth are briefly discussed.     

Vertical pressure profile of Titan—observations of the PPI/HASI instrument

The Huygens entry probe descended through the atmosphere of Titan and provided an excellent set of observations of the atmosphere and the surface of Titan. During the 150-min descent the Huygens Atmospheric Structure Instrument (HASI) observed a comprehensive set of variables, including pressure, temperature, density and atmospheric electricity. The atmospheric pressure profile was recorded by the Pressure Profile Instrument (PPI), provided by Finnish Meteorological Institute (FMI). The instrument started measurements at an altitude of 150 km, and produced about 28 bits of data per second. Data were also obtained through the time of 31 min beyond the time of surface impact. The first-order scientific analysis of the PPI results has been performed. The observations together with hydrostatic assumption and in combination with other measurements have provided the first atmospheric pressure profile and the surface pressure (of approximately ) for Titan's atmosphere. To carry out the pressure profile reconstruction we developed a real gas formulation, which is applicable also for other Titan atmospheric investigations. The altitude versus time speed of the descent was calculated and the results were compared with the direct altitude observations by the radar altimeter during the last 40 km of the descent. The fit was excellent demonstrating the high-quality level of the PPI observations as well as the utilized investigation methods.     

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.