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.     

New insights into Titan's organic chemistry in the gas and aerosol phases.

Titan, the largest satellite of Saturn, with a dense atmosphere very rich in organics, and many couplings in the various parts of its "geofluid", is a reference for studying prebiotic chemistry on a planetary scale. New data have been obtained from experiments simulating this organic chemistry (gas and aerosol phases), within the right ranges of temperature and a careful avoiding of any chemical contamination. They show a very good agreement with the observational data, demonstrating for the first time the formation of all the organic species already detected in Titan atmosphere including, at last, C4N2, together with many other species not yet detected in Titan. This strongly suggests the presence of more complex organics in Titan's atmosphere and surface, including high molecular weight polyynes and cyanopolyynes. The NASA-ESA Cassini-Huygens mission has been successfully launched in October 1997. The Cassini spacecraft will reach the Saturn system in 2004 and become an orbiter around Saturn, while the Huygens probe will penetrate into Titan's atmosphere. In situ measurements, in particular from Huygens GC-MS and ACP instruments, will provide a detailed analysis of the organics present in the air, aerosols, and surface. This very ambitious mission should yield much information of crucial importance for our knowledge of the complexity of Titan's chemistry, and, more generally for the field of exobiology.     

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.     

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.     

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.     

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.     

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N₂/0.1 CH₄ gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n (1.65) and k (0.004 to 0.08) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k(λ), including the 4.6 μm nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.     

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.     

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.     

Synthesis,chemistry and photochemistry of cyanobutadiyne (HCCCCCN)

Cyanobutadiyne has been synthesized starting from the mono or bistributylstannyl derivative of 1,3-butadiyne and p-toluenesulfonyl cyanide. The UV spectrum of HC₅N and the ¹³C NMR spectrum of the deuterocyanobutadiyne DC₅N have been recorded for the first time. Cyanobutadiyne has been detected in the photolysis of mixtures of gases observed on Titan. Its formation starting from cyanoacetylene and acetylene also occurs in the presence of huge amounts of dinitrogen, the major constituent of the Titan’s atmosphere. The application of these findings to the atmosphere of Titan is discussed. The chemistry and photochemistry of cyanobutadiyne have been investigated. A photoadduct has been observed in the photolysis of cyanoacetylene and ethanethiol and, a univocal synthesis of this compound was performed by a nucleophilic addition reaction.     

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.     

IR and UV spectroscopic data for polyynes: predictions for long carbon chain compounds in Titan's atmosphere.

A better understanding of the complex organic chemistry occurring in the methane rich atmosphere of Titan can be achieved via the comparison of observations with results obtained by theoretical models. Available observations are still few but their analysis requires the knowledge of a large set of data, namely frequencies and absolute band intensities. Cross sections are also needed to develop the chemical schemes of photochemical models, in particular the schemes leading to the formation of haze particles visible on Titan. Unfortunately, some of these parameters are not well known, especially if one takes into account the extreme physical conditions of the studied object. This lack of data is particularly enhanced for polyynes because these compounds are highly unstable at the usual pressure and temperature conditions of a laboratory and therefore are very difficult to study. We have developed UV and IR studies, coupling experimental and theoretical approaches, in order to extrapolate the parameters available for short polyynes to longer carbon chains. In the mid-UV range, when the length of the chain increases, the absorption system of polyynes is shifted to longer wavelength and its oscillator strength increases linearly. In the IR range, with the increase of the number of carbon bonds, the positions of the CCC and CCH bending modes shift to lower energy, the latest converging rapidly to a fixed value of 620.5 cm-1 for an infinite length polyyne. Implications for detection and evolution of polyynes in Titan's atmosphere are emphasised.     

气溶胶光学特性偏振遥感反演算法

陆地上空大气顶的辐射主要由大气散射和地表反射组成,一般地表反射的贡献要大于大气散射的贡献,使得陆地上空气溶胶的特性提取非常困难,而偏振信息只强烈依赖于散射粒子的特性,发展基于偏振信息的气溶胶反演方法是非常有效的. 通过对矢量辐射传输方程求解进行研究,基于倍加累加法矢量辐射传输模式分析影响气溶胶反演的主要因素,确定多维参数查找表建立方法,利用POLDER(Polarization and Directionality of the Earth-s Reflectances)提供的反射率和偏振反射率数据,发展了一种利用反射率和偏振反射率查找表迭代查找反演气溶胶光学参数和地表反射率的算法,实现了对北京、香河、Dalanzadgad观测站上空气溶胶光学厚度、粒子半径、折射指数和地表反射率的反演.用AERONET(Aerosol Robotic Network)地基数据对反演结果进行了验证.     

Titan's atmosphere composition: certainties and speculations.

Firm results concerning the thermal structure, the composition, the seasonal effects of the atmosphere of Titan, as well as the superotation of its stratosphere are reviewed. The nature of the surface of the satellite, the possible presence of argon in the atmosphere and the structure and composition of clouds and aerosols are, among other topics, still speculative. The implications of the observed deuterium enrichment on the origin of ices in the outer part of the nebula are controversial.     

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.     

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.     

Stability and mass flow in Saturn's rings

Besides gravitational effects, interesting electrodynamical processes could also take place in the vicinity of the rings of Saturn. In part, this is because of the electrostatic charging of the ring particles by the magnetospheric and ionospheric plasma, and in part, the generation of impact plasma by meteoroid bombardment at the ring plane could lead to strong coupling between the rings and the ionosphere via a variety of current systems. The mass transport and angular momentum transfer in association with the ring-ionosphere coupling may cause quite large changes in the ring configuration over the age of the solar system. The presence of the sharp boundary between the B and the C rings perhaps is a good example. To highlight these new developments, we describe several of the electrodynamical mechanisms (with emphasis on their corresponding electric fields and current systems) which have been postulated to be of importance in determining the mass transport of the ring system. Further points are made that, besides mass exchange between the rings and the planetary atmosphere, the mass injection from the rings could also have significant effect on the mass and energy budget of the magnetosphere, maintenance of the E ring, the Titan hydrogen torus as well as aeronomic process in the upper atmosphere of Titan.     

Space station gas-grain simulation facility: Application to exobiology

The Space Station provides an environment in which the forces required to suspend particles during an experiment can be reduced by as much as six orders of magnitude. This reduction in levitation force enables us to perform many new experiments in a variety of disciplines. We have grouped these experiments into two catatgories: 1) those involving an individual particle or the interaction between a few particles and 2) those involving clouds of particles. We consider only particle experiments at this stage because cloud experiments suffer from electrostatic interactions and levitation-forced coalescence therefore requiring considerably more space, mass and crew interaction. The displacement of a particle resulting from g-jitter for ballistic, Knudsen and Stokes flow regimes is considered in detail and the radiation, acoustic, electrostatic and electromagnetic levitation mechanisms to control this motion are reviewed. We have selected the simulation of organic haze production on Titan as an example experiment for detailed study. The objective of this experiment is to simulate the photolysis of methane and the subsequent formation of the organic haze particles in the upper atmosphere of Titan.     

Microgravity particle research on the space station: the Gas-Grain Simulation Facility.

In the gravitational field on Earth, the large settling rate of micron-sized particles and the effects of gravity-induced convection prohibit many interesting studies of phenomena such as coagulation, collisions, and mutual interactions of droplets, dust grains and other particles. Examples of exobiology experiments involving these phenomena are the simulation of organic aerosol formation in Titan's atmosphere, studies of the role of comets in prebiotic chemical evolution, and simulations of carbon grain interactions in various astrophysical environments. The Gas-Grain Simulation Facility (GGSF) is a proposed Earth-orbital laboratory that will allow present ground-based experimental programs which study processes involving small particles and weak interactions to be extended to a new domain. Physics issues that scientists wishing to propose GGSF experiments must consider are reviewed in this paper. Specifically, coagulation, motion in gases and vacua, and wall deposition of particles in a microgravity environment are discussed.     

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.