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.     

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.     

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.     

Voyager photopolarimeter observations of Saturn and Titan

The Voyager 2 photopolarimeter experiment observed the intensity and polarization of scattered sunlight from the atmospheres of Saturn and Titan in the near-UV at 2640 Å and in the near-IR at 7500 Å. Measurements of Saturn's limb brightening and polarization at several phase angles up to 70° indicate that a significant optical depth of UV absorbers are present in the top 100 mbar of Saturn's atmosphere in the Equatorial Zone and north polar region, and possibly at other latitudes as well. UV absorbers are prominent in polar regions, suggesting that charged particle precipitation from the magnetosphere may be important in their formation.The whole-body polarization of Titan is strongly positive in both the UV and near IR. If spherical particles are responsible for the polarization, no single size distribution or refractive index can account for the polarization at both wavelengths. The model atmosphere proposed by Tomasko and Smith [1], characterized by a gradient in particle size with altitude, seems capable of explaining the Voyager observations. If non-spherical particles predominate, the Voyager observations place important constraints on their scattering properties.     

Analytical pyrolysis experiments of Titan aerosol analogues in preparation for the Cassini Huygens mission.

Comparative pyrolysis mass spectrometric data of Titan aerosol analogues, called "tholins", are presented. The Titan tholins were produced in the laboratory at Cornell by irradiation of simulated Titan atmospheres with high energy electrons in plasma discharge. Mass-spectrometry measurements were performed at FOM of the solid phase of various tholins by Curie-point pyrolysis Gas-Chromatography/Mass-Spectrometry (GCMS) and by temperature resolved in source Pyrolysis Mass-Spectrometry to reveal the composition and evolution temperature of the dissociation products. The results presented here are used to further define the ACP (Aerosol Collector Pyrolyser)-GCMS experiment and provide a basis for modelling of aerosol composition on Titan and for the interpretation of Titan atmosphere data from the Huygens probe in the future.     

Comparison of methods for the determination of key reactions in chemical systems: Application to Titan’s atmosphere

A new paradigm is emerging in the field of photochemistry modeling in giant planets and Titan atmospheres. The emphasis is placed on the accurate predictions of the models and the quantification of their uncertainties. In order to improve photochemical models predictions, it is necessary to identify in chemical schemes the key reactions that should be studied in priority at conditions relevant to planetary atmospheres.     

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.     

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.     

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.     

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.     

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.     

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.     

近地环境的电状态

通过电过程的耦合是太阳对气象耦合影响的机制之一,本文扼要地综述了迄今为止人们对近地环境内电流和电场的观测结果以及在此基础上所建立的经验和理论模式;给出了在平均状况下和太阳活动下近地环境电性能的总概貌,重点在靠近地球表面的低层、中层大气区域;着重介绍了该区域内的大气电性能及其受太阳活动的调制.      

Proposed ozone reference models for the middle atmosphere

Since the publication of the last COSPAR International Reference Atmosphere (CIRA 72), large amounts of ozone data acquired from satellites have become available in addition to increasing quantities of rocketsonde, balloonsonde, Dobson, M83, and Umkehr measurements. From the available archived satellite data, models are developed for the new CIRA using 5 satellite experiments (Nimbus 7 SBUV and LIMS, AEM-2 SAGE, and SME IR and UVS) of the monthly latitudinal and altitudinal variations in the ozone mixing ratio in the middle atmosphere. Standard deviations and interannual variations are also quantified. The satellite models are shown to agree well with a previous reference model based on rocket and balloon measurements.     

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.     

Determination of surface parameters and fluxes for climate studies from space observation. Methods,results and problems

Climate being the result of many interconnected processes, it can hardly be understood without models which describe these various processes as quantitatively as possible and define the parameters which are relevant for climate studies. Among those, surface processes and therefore surface parameters are now recognized to be of great importance. Some examples are discussed in the first part, showing the great interest to measure the relevant parameters on a multi-year basis, over large areas with sufficiently dense array and on a stable basis, in order to monitor climate changes or to study the impact on climate of the modifications of some relevant parameters which are analysed. Since space observations from satellites fulfil these requirements, it is clear that they will become very soon a fundamental tool for climate studies. Unfortunately, as it is discussed in the second part, satellites do measure only spectral radiances at the top of the atmosphere and the determination of the relevant surface parameters (or fluxes) from these radiances still raises many problems which have to be solved, although many progresses have already been made.The aim of this paper is therefore to review and discuss these problems and the various ways they have been tackled until now. The first part is devoted to an overview of what needs to be measured and why, while the existing methods for determining the most important surface parameters from space observations are presented in the second part where a particular attention is given to the theoretical and experimental validations of these methods, their limits and the problems still to be solved.     

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.     

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.     

A gas management system for an ultra long duration Titan blimp

This paper presents analyses, designs and experimental results for the gas management system of a hydrogen-filled blimp capable of flying in the lower atmosphere of Titan for a period of 1 year or more. The engineering strategy has two basic elements: first, to minimize leakage rates from the blimp envelope and ballonets; and second, to provide auxiliary subsystems to mitigate the life-limiting effects resulting from those leaks. Leak minimization is achieved through use of cryogenically compatible balloon materials and adhesives, and selection of ballonet geometries that minimize pinhole generation via folding and material fatigue. Hydrogen loss to the environment through leaks in the blimp envelope is compensated by producing new hydrogen through chemical processing of atmospheric methane. Nitrogen leaked into the blimp from the ballonets is removed by a carbon absorption system and periodically vented to the atmosphere. Data is presented on the measured leak rate from a full scale (13 m long) prototype blimp envelope and on the performance of a low mass, low power prototype device that generates hydrogen from methane. These results are factored in to an overall system design that quantifies the mass and power requirements for a minimum 1 year operational lifetime.