The low temperature organic chemistry of Titan's geofluid.

Organic chemistry on Titan and prebiotic chemistry on Earth involve the same N-containing organics: nitriles and their oligomers. Couplings of their chemistry in the three parts of Titan's geofluid (atmosphere, aerosols and surface) seem to play a key role in the organic chemical evolution of the planet. If liquid water was present on Titan, then a prebiotic chemistry, involving eutectics, similar to that of the early Earth, may have occurred. However, liquid water is currently absent and a prebiotic chemistry based only on N-organics may be evolving now on Titan. The other consequence of the low temperatures of Titan is the possible formation of organics unstable at room temperature and very reactive. So far, these compounds have not been systematically searched for in experimental studies of Titan's organic chemistry. C4N2 has already been detected on Titan. Powerful reactants in organic chemistry, CH2N2, and CH3N3, may be also present. They exhibit spectral signatures in the mid-IR strong enough to allow their detection at the 10-100 ppb level. They may be detectable on future IR spectra (ISO and Cassini) of Titan.     

Organic chemistry in Titan's atmosphere: new data from laboratory simulations at low temperature.

Many experiments have already been carried out to simulate organic chemistry on Titan, the largest satellite of Saturn. They can provide fruitful information on the nature of minor organic constituents likely to be present in Titan's atmosphere, both in gas and aerosol phases. Indeed, all the organic compounds but one 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, and polyynes, first of all C6H2, have never been detected in experimental simulation thus far. All these compounds are thermally unstable, and the temperature conditions used during the simulation experiments were not appropriate. We have recently started a new program of simulation experiments with temperature conditions close to that of Titan's environment. It also uses dedicated analytical techniques and procedures compatible with the analysis of organics only stable at low temperatures, as well solid products of low stability in the presence of O2 and H2O. Spark discharge of N2-CH4 gas mixtures was carried out at low temperature in the range 100-150 K. Products were analysed by FTIR, GC and GC-MS techniques. GC-peaks were identified by their mass spectrum, and, in most cases, by comparison of the retention time and mass spectrum with standard ones. We report here the first detection in Titan simulation experiments of C6H2 and HC5N. Their abundance is a few percent relative to C4H2 and HC3N, respectively. Preliminary data on the solid products indicate an elemental composition corresponding to (H11C11N)n. These results open new prospects in the modeling of Titan's haze making.     

Surface-atmosphere interactions on Titan compared with those on the pre-biotic Earth.

The surface and atmosphere of Titan constitute a system which is potentially as complex as that of the Earth, with the possibility of precipitation, surface erosion due to liquids, chemistry in large surface or subsurface hydrocarbon reservoirs, surface expressions of internal activity, and occasional major impacts leading to crustal melting. While none of the above have been observed as yet, the composition, density and thermal properties of Titan's atmosphere make it uniquely suited in the outer solar system as a place where such processes may occur. The one attribute of the Earth not expected on Titan is biological activity, which has had a profound effect on the evolution of the Earth's surface-atmosphere system. The earliest environment of Titan could have been warm enough for liquid ammonia-water solutions to exist on or near surface; pre-biotic organic processes may have taken place in such an environment. After a few hundred million years surface ammonia-water would have disappeared. Therefore, study of Titan through the Cassini-Huygens mission, planned for launch in 1997, primarily affords the opportunity to understand planet-wide surface-atmosphere interactions in the presence of fluids but in the absence of life. More speculative is the possibility that endogenic and exogenic heating continue to provide short-lived environments on Titan wherein pre-biotic organic processes in the presence of water happen.     

The physical nature of Titan's aerosols: laboratory simulations.

The atmosphere of Titan is known to contain aerosols, as evidenced by the Voyager observations of at least three haze layers. Such aerosols can have significant effects on the reflection spectrum of Titan and on the chemistry and thermal structure of its atmosphere. To investigate some of these effects, laboratory simulations of the chemistry of Titan's atmosphere have been done. The results of these studies show that photolysis of acetylene, ethylene, and hydrogen cyanide, known constituents of Titan's atmosphere, yields sub-micron sized spheres, with mean diameters ranging from 0.4 to 0.8 microns, depending on the pressures of the reactant gases. Most of the spheres are contained in near-linear aggregates. The formation of the aggregates is consistent with models of Titan's reflection spectrum and polarization, which are best fit with non-spherical particles. At room temperature, the particles are very sticky, but their properties at low temperatures on Titan are presently not known.     

Shumann resonances and electromagnetic transparence in the atmosphere of Titan

Among the multiple questions that the CASSINI/HUYGENS mission tries to answer is the likelihood of electric discharges in Titan's atmosphere. The instruments “Huygens Atmospheric Structure Instrument” and “Radio and Plasma Wave Science” will probe the electromagnetic emissions during the Huygens descent and Cassini flybys, respectively. Although no lightning was observed during Voyager's encounters with Titan in 1980 and 1981, this does not exclude the existence of lightning phenomena. Recent investigations show that lightning discharges could occur in the lower atmosphere, such as the detection of methane condensation clouds in the troposphere and the theoretical prediction of an electric field that would be sufficient enough to cause lightning. We present a numerical model of Titan's atmosphere with the aim of calculating the resonance frequencies and the atmospheric transparency to electromagnetic waves. The detection and measurement of these resonances, Schumann frequencies, by the Huygens probe, would show the existence of electric activity connected with lightning discharges in the atmosphere. As it happens with the Schumann frequencies of Earth, losses associated with the electric conductivity will make these frequencies to be lower than the theoretically predicted, the fundamental one being located between 11 and 15 Hz. An analytical study shows that the strong losses associated with the high conductivity make it impossible that an electromagnetic wave generated near the surface with a frequency of 10 MHz or lower reaches the outer part of Titan's atmosphere. Therefore the detection of electromagnetic waves coming from Titan's lower atmosphere by the RPWS instrument is very unlikely.     

Photochemical growing of complex organics in planetary atmospheres

UV induced syntheses of organic compounds from the main atmospheric constituents can be a very important source of organics in a given planetary environment provided the atmosphere is in a reduced state. The evolution of a CO₂ rich medium only produces very low yields of formaldehyde and related oxygenated compounds. Considering a CO rich atmosphere, the photochemical yield of O-organics formation is much higher, when the synthesis of N-organics remains difficult. The most favourable atmosphere as far as photochemical organic synthesis is concerned is a CH₄ rich milieu.. The photochemical evolution of such a CH₄ atmosphere under UV irradiation leads to a chain of various organics, the complexity of which increases together with the number of pathways involved in their formation. Their complexity also closely correlates with their UV photoabsorption spectrum: the more complex they are, the more shifted is their UV spectrum toward the visible range. Direct photodissociation of methane requires UV photon of wavelengths shorter than about 145 nm. It mainly produces ethane which absorbs UV at wavelengths shorter than about 160 nm, and acetylene, that presents an absorption spectrum extending up to 200 nm. This shift still continuously increases with further increase in number of C atoms. Unsaturated hydrocarbons with 4 and more C atoms have UV absorption characteristics including noticeable band structures in the 250–300 nm range. This trend has very important implication in the photochemical behaviour of a CH₄-rich planetary atmosphere, as it induces many catalytic processes. The occurrence of such processes is closely related to vertical atmospheric and energy deposition profiles. Titan provides a very good example of such a UV-directed organic atmospheric chemistry.     

Search for organic molecules in the outer solar system

Recent developments of millimeter astronomy have led to the discovery of more and more complex molecules in the interstellar medium. In a similar way, attempts have been made to detect complex molecules in the atmospheres of the most primitive bodies of the Solar System, i.e. outer planets and comets, as well as in Titan's atmosphere. An important progress has been achieved thanks to the continuous development of infrared astronomy, from the ground and from space vehicles. In particular, an important contribution has come from the IRIS-Voyager infrared spectrometer with the detection of prebiotic molecules on Titan, and some complex organic molecules on Jupiter and Saturn. Another important result has been the observation of carbonaceous material in the immediate surroundings of Comet Halley's nucleus. In the near future, the search for organic molecules in the outer Solar System should benefit from the developments of large millimeter antennae, and in the next decade, from the operation of infrared Earth-orbiting spacecrafts (ISO, SIRTF).     

Corona discharge of Titan's troposphere.

The atmosphere of Titan is constantly bombarded by galactic cosmic rays and Saturnian magnetospheric electrons causing the formation of free electrons and primary ions, which are then stabilized by ion cluster formation and charging of aerosols. These charged particles accumulate in drops in cloud regions of the troposphere. Their abundance can substantially increase by friction, fragmentation or collisions during convective activity. Charge separation occurs with help of convection and gravitational settling leading to development of electric fields within the cloud and between the cloud and the ground. Neutralization of these charge particles leads to corona discharges which are characterized by low current densities. These electric discharges could induce a number of chemical reactions in the troposphere and hence it is of interest to explore such effects. We have therefore, experimentally studied the corona discharge of a simulated Titan's atmosphere (10% methane and 2% argon in nitrogen) at 500 Torr and 298 K by GC-FTIR-MS techniques. The main products have been identified as hydrocarbons (ethane, ethyne, ethene, propane, propene + propyne, cyclopropane, butane, 2-methylpropane, 2-methylpropene, n-butene, 2-butene, 2,2-dimethylpropane, 2-methylbutane, 2-methylbutene, n-pentane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, 2,2-dimethylhexane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, 2,3-dimethylpentane and n-heptane), nitriles (hydrogen cyanide, cyanogen, ethanenitrile, propanenitrile, 2-methylpropanenitrile and butanenitrile) and an uncharacterized film deposit. We present their trends of formation as a function of discharge time in an ample interval and have derived their initial yields of formation. These results clearly demonstrate that a complex organic chemistry can be initiated by corona processes in the lower atmosphere. Although photochemistry and charged particle chemistry occurring in the stratosphere can account for many of the observed hydrocarbon species in Titan, the predicted abundance of ethene is to low by a factor of 10 to 40. While some ethene will be produced by charged-particle chemistry, its production by corona processes and subsequent diffusion into the stratosphere appears to be an adequate source. Because little UV penetrates to the lower atmosphere to destroy the molecules formed there, the corona-produced species may be long-lived and contribute significantly to the composition of the lower atmosphere and surface.     

Possible contribution of different energy sources to the production of organics in Titan's atmosphere.

A quantitative comparison of the products arising from the irradiation of a Titan's simulated atmosphere is presented. The energy sources used represent some of the main events that occur in the satellite's atmosphere. All of the compounds identified are classified in the hydrocarbon and nitrile chemical families. Almost all of the detected compounds in Titan's atmosphere are produced by one or more energy sources. The compounds with the highest energy yields include the C2 hydrocarbons, methanonitrile and ethanonitrile. The possibility of using some of the produced organics as tracer compounds during the Huygens descend to identify the leading energy form in the different atmospheric levels remains open.     

The escape of molecular hydrogen and the synthesis of organic nitriles in planetary atmospheres.

What is the influence of hydrogen escape from the atmosphere of small planetary bodies on the synthesis of organic molecules in that atmosphere? To answer this question, laboratory experiments have been performed to study the evolution of different reducing model atmospheres submitted to electrical discharges, with and without the simulation of H₂ escape. A study of mixtures of nitrogen and methane shows a very strong effect of H₂ escape on the formation of organic nitriles, the only nitrogen containing organics detected in the gas phase. These are HCN, CH  CCN, (CN)₂, CH₂CHCN, CH₃ CN and CH₃CH₂CN. The yield of synthesis of most of these compounds is noticeably increased, up to several orders of magnitude, when hydrogen escape is simulated. The escape of H₂ from the atmosphere of the primitive Earth may have played a crucial role in the formation of reactive organic molecules such as CHCCN or (CN)₂, which can be considered as important prebiotic precursors. These experimental results may also explain extant data concerning the nature and relative abundance of organics present in the atmosphere of Titan, a planetary satellite which may be an ideal model within our solar system for the study of organic cosmochemistry and exobiology.     

New planetary atmosphere simulations: application to the organic aerosols of Titan.

The atmosphere of Titan partly consists of hazes and aerosol particles. Experimental simulation is one of the powerful approaches to study the processes which yield these particles, and their chemical composition. It provides laboratory analogues, sometimes called tholins. Development and optimization of experimental tools were undertaken in order to perform chemical and physical analyses of analogues under conditions free from contamination. A "Titan aerosol generator" was developed in the frame of the Cassini-Huygens mission, in order to produce Titan's aerosol analogues within conditions closer to those of the titanian atmosphere: cold plasma simulation system, low pressure and low temperature. The direct current (DC) glow discharge is produced by applying a DC voltage between two conductive electrodes inserted into the gas mixture-model of the studied atmosphere- at low pressure. A high-impedance power supply is used to provide the electrical field. All the system is installed in a glove box, which protect samples from any contamination. Finally the research program expected with this new material is presented.     

Titan on the eye of voyager encounter

A decade of intense scientific study of Titan is reviewed. The atmosphere is not well understood at the time of this writing, but it is confidently expected that great progress will be made by the Voyager spacecraft now en route to the Saturn System.     

A facility for simulating Titan’s environment

As a result of measurements acquired by the Cassini–Huygens mission of Titan’s near surface atmospheric composition and temperature, Titan conditions can now be simulated in the laboratory and samples can subsequently be subjected to those conditions. Titan demonstrates an active hydrological-like cycle with its thick atmosphere, dynamic clouds, polar lakes of methane and ethane, moist regolith, and extensive fluvial erosive features. Unlike Earth, Titan’s hydrological-like cycle likely involves several constituents, primarily methane and ethane. Here the properties of a new Titan simulation facility are presented, including conceptual methodology, design, implementation, and performance results. The chamber maintains Titan’s surface temperature and pressure, and the sample cryogenic liquids undergoing experimentation are condensed within the chamber itself. During the experiments, the evaporation rates of the sample liquids are directly determined by continually measuring mass. Constituents are analyzed utilizing a Fourier Transform Infrared Spectroscopy (FTIR), and vapor concentrations are determined using a gas chromatograph fitted with a Flame Ionization Detector (FID). All pertinent data is logged via computer. Under laboratory conditions, the direct measurements of the evaporation rates of methane, ethane, and mixtures thereof can be achieved. Among the processes to be studied are the effects of regolith on transport from the subsurface to the atmosphere, the freezing point depression effects of dissolved nitrogen, and the solubility of various relevant organic compounds.     

Pioneer fly-by of Saturn and its rings

We report results from analysis of data from Pioneer Saturn's Imaging Photopolarimeter. These include the discovery of a new ring and satellite, the structure of the atmosphere of Saturn and Titan, the inhomogeneous nature of Saturn's rings, and a model for the rings' formation and bimodal particle size distribution.     

How primitive are the gases in Titan's atmosphere?

Titan's atmosphere contains a mixture of nitrogen, methane, argon, hydrogen, simple hydrocarbons and nitriles, carbon monoxide, and carbon dioxide. Sources of nitrogen may be as a product of the photodissociation of ammonia or trapped in the ices that formed the satellite. Reasons for the abundance of deuterium are examined and its association with nitrogen on Titan is explained.     

From the interstellar clouds, through the inner to the outer solar system: a universally distributed complex organic chemistry. Preface.

High molecular weight organic compounds are involved in the chemistry and physics of many astrophysical and planetary objects. They are or should be present in interstellar dust, in comets and meteorites, in the Giant planets and Titan, in asteroids Triton and icy satellites. They represent a class of very complex organic material, part of which may have played a role in the origin of life on Earth. Thus they directly concern prebiotic chemistry and exobiology.     

Solid organic matter in the atmosphere and on the surface of outer Solar System bodies.

Many bodies in the outer Solar System display the presence of low albedo materials. These materials, evident on the surface of asteroids, comets, Kuiper Belt objects and their intermediate evolutionary step, Centaurs, are related to macromolecular carbon bearing materials such as polycyclic aromatic hydrocarbons and organic materials such as methanol and related light hydrocarbons, embedded in a dark, refractory, photoprocessed matrix. Many planetary rings and satellites around the outer gaseous planets display such component materials. One example, Saturn's largest satellite, Titan, whose atmosphere is comprised of around 90% molecular nitrogen N2 and less than 10% methane CH4, displays this kind of low reflectivity material in its atmospheric haze. These materials were first recorded during the Voyager 1 and 2 flybys of Titan and showed up as an optically thick pinkish orange haze layer. These materials are broadly classified into a chemical group whose laboratory analogs are termed "tholins", after the Greek word for "muddy". Their analogs are produced in the laboratory via the irradiation of gas mixtures and ice mixtures by radiation simulating Solar ultraviolet (UV) photons or keV charged particles simulating particles trapped in Saturn's magnetosphere. Fair analogs of Titan tholin are produced by bombarding a 9:1 mixture of N2:CH4 with charged particles and its match to observations of both the spectrum and scattering properties of the Titan haze is very good over a wide range of wavelengths. In this paper, we describe the historical background of laboratory research on this kind of organic matter and how our laboratory investigations of Titan tholin compare. We comment on the probable existence of polycyclic aromatic hydrocarbons in the Titan Haze and how biological and nonbiological racemic amino acids produced from the acid hydrolysis of Titan tholins make these complex organic compounds prime candidates in the evolution of terrestrial life and extraterrestrial life in our own Solar System and beyond. Finally, we also compare the spectrum and scattering properties of our resulting tholin mixtures with those observed on Centaur 5145 Pholus and the dark hemisphere of Saturn's satellite Iapetus in order to demonstrate the widespread distribution of similar organics throughout the Solar System.     

An aerobot for global in situ exploration of Titan

This paper describes the design and component testing of an aerobot that would be capable of global in situ exploration of Saturn’s moon, Titan, over a 6–12 month mission lifetime. The proposed aerobot is a propeller-driven, buoyant vehicle that resembles terrestrial airships. However, the extremely cold Titan environment requires the use of cryogenic materials of construction and careful thermal design for protection of temperature-sensitive payload elements. Multiple candidate balloon materials have been identified based on extensive laboratory testing at 77 K. The most promising materials to date are laminates comprised of polyester fabrics and/or films with areal densities in the range of 40–100 g/m². The aerobot hull is a streamlined ellipsoid 14 m in length with a maximum diameter of 3 m. The enclosed volume of 60 m³ is sufficient to float a mass of 234 kg at a maximum altitude of 8 km at Titan. Forward and aft ballonets are located inside the hull to enable the aerobot to descend to the surface while preserving a fully inflated streamlined shape. Altitude changes are effected primarily through thrust vectoring of the twin main propellers, with pressure modulated buoyancy change via the ballonets available as a slower backup option. A total of 100 W of electrical power is provided to the vehicle by a radioisotope power supply. Up to half of this power is available to the propulsion system to generate a top flight speed in the range of 1–2 m/s. This speed is expected to be greater than the near surface winds at Titan, enabling the aerobot to fly to and hover over targets of interest. A preliminary science payload has been devised for the aerobot to give it the capability for aerial imaging of the surface, atmospheric observations and sampling, and surface sample acquisition and analysis. Targeting, hovering, surface sample acquisition and vehicle health monitoring and automatic safing actions will all require significant on-board autonomy due to the over 2 h round trip light time between Titan and Earth. An autonomy architecture and a core set of perception, reasoning and control technologies is under development using a free-flying airship testbed of approximately the same size as the proposed Titan aerobot. Data volume from the Titan science mission is expected to be on the order of 100–300 Mbit per day transmitted either direct to Earth through an 0.8 m high gain antenna or via an orbiter relay using an omni-directional antenna on the aerobot.     

Titan: some new results.

New analyses of Voyager spectra of Titan have led to improvements in the determination of abundances of minor constituents as a function of latitude and altitude. Ground-based microwave observations have extended the Voyager results for HCN, and have demonstrated that CO is mysteriously deficient in the stratosphere. The origin of the CH4, CO, and N2 in Titan's atmosphere is still unresolved. Both primordial and evolutionary sources are compatible with the available evidence.     

Production of hydrocarbons and nitriles by electrical processes in Titan's atmosphere.

Although lightning has not been observed in Titan's atmosphere, the presence of methane rain in the troposphere suggests the possibility of electrical activity in the form of corona and/or lightning discharges. Here we examine the chemical effects of these electrical processes on a Titan simulated atmosphere composed of CH4 in N2 at various mixing ratios. Corona discharges were simulated in two different experimental arrays. For the detection of reactive intermediates we used a mass spectrometer to study the main positive ions arising by bombarding low-energy electrons from a hot filament into low-pressure methane. The final stable products, generated by applying a high voltage in a coaxial reactor with either positive or negative polarity, were separated and detected by gas chromatography-Fourier transform infrared spectroscopy and electron impact mass spectrometry (GC-FTIR-MS). Lightning discharges were simulated by a hot and dense plasma generated by a Nd-YAG laser and the final products were separated and detected by GC-FTIR-MS. Corona discharges produce linear and branched hydrocarbons as well as nitriles whereas lightning discharges generate mainly unsaturated hydrocarbons and nitriles. Lightning discharges are about 2 orders of magnitude more efficient in product formation than corona discharges.