David Coscia

Experimental laboratory simulation of Titan's atmosphere: aerosols and gas phase

The discovery that Titan, the largest satellite of Saturn, has an atmosphere and that methane is a significant constituent of it, was the starting point for a systematic study of Titan’s atmospheric organic chemistry. Since then, the results from numerous ground-based observations and two flybys of Titan, by Voyager I and II, have led to experimental laboratory simulation studies and photochemical and physical modeling. All these works have provided a more detailed picture of Titan. We report here a continuation of such a study performing an experimental laboratory simulation of Titan’s atmospheric chemistry, and considering the two physical phases involved: gases and aerosols. Concerning the gaseous phase, we report the first detection of C4N2 and we propose possible atmospheric abundances for 70 organic compounds on Titan’s upper atmosphere. Concerning the solid phase, we have characterized aerosol analogues synthesized in conditions close to those of Titan’s environment, using elemental analysis, pyrolysis, solubility studies and infrared spectroscopy. # 1999 Elsevier Science Ltd. All rights reserved.

Complex organic matter in Titan's atmospheric aerosols from in situ pyrolysis and analysis.

Aerosols in Titans atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titans aerosols by pyrolysis at 600 °C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols.

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 Titans atmosphere, both in gas and aerosol phases. Indeed, all the organic compounds but one already detected in Titans 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 Titans 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 Titans haze making.

REVIEW AND LATEST RESULTS OF LABORATORY INVESTIGATIONS OF TITAN'S AEROSOLS

Titan, the largest satellite of Saturn, has an atmosphere chiefly made up of N2 and CH4, and including many organics. This atmosphere also partly consists of hazes and aerosol particles which shroud the surface of this satellite, giving it a reddish appearance. The aerosols observed in Titans atmosphere are thought to be synthesized at high altitudes (>300 km) and fall to the surface. Varying with temperature profiles, condensation phenomena take place in the lower atmosphere, about 100 km below. These solid particles, often called ‘tholins’, have been currently investigated for many years by laboratory scientists and physics modellers. This paper assesses past research and results in different fields (elemental composition, optical constants, pyrolysis, particle size), highlighting interests and questions aroused by these studies. It also presents the latest results and advances, and concludes with existing problems and future pathways.

Gas chromatography in space exploration capillary and micropacked columns for in situ analysis of Titan's atmosphere

Abstract The gas chromatography–mass spectrometry (GC–MS) experiment using capillary and micropacked columns is one of the main instruments of the Huygens probe of the Cassini–Huygens mission launched in October 1997 for the in situ analysis of Titan’s atmosphere. Because of its composition and density the study of the atmosphere of Titan is of primary interest for understanding the prebiotic chemistry in the primitive Earth’s environment. We describe here the GC subsystem of the GC–MS instrument with a particular emphasis on its exobiological implications. The GC subsystem includes three columns which operate in parallel: a carbon molecular sieve micropacked column is used for the separation of CO, N2 and other permanent gases; a capillary column will separate the light hydrocarbons up to C3; a second capillary column with a cyanopropyl dimethyl polysiloxane stationary phase will analyze the C4–C8 hydrocarbons and the low-molecular mass nitriles up to C4. These heavier compounds will mainly result from the pyrolysis of the aerosols present in the atmosphere of Titan by using the aerosol collector pyrolyser instrument.

An exobiological view of Titan and the Cassini-Huygens mission

Abstract The largest satellite of Saturn, Titan, is the only one in the solar system having a dense atmosphere. In many aspects it is similar to the Earth. Moreover, organic chemistry on Titan and prebiotic chemistry on Earth involve the same N-containing organic molecules: nitriles, including acetylenic nitriles and dinitriles, and their oligomers. Thus, in spite of much lower temperatures and the absence of liquid water, because of its environment very rich in organics, and the many couplings involved in the various parts of its “geofluid”, Titan is a reference laboratory for studying prebiotic chemistry on a planetary scale. In the frame of the NASA-ESA Cassini-Huygens mission, which includes an orbiter (Cassini) around Saturn and a probe (Huygens) in Titans atmosphere, organic chemistry in Titans “geofluid” will be studied in great detail. In situ measurements, in particular from Huygens GC-MS and ACP instruments, will provide detailed analysis of the organics present in the air, aerosols, and surface. The mission will be launched in october 1997, for an arrival in the Saturn System in 2004. Thus, at horizon 2000, we can expect many information of crucial importance for the field of exobiology.

Gas chromatography for in situ analysis of a cometary nucleus. II. Analysis of permanent gases and light hydrocarbons with a carbon molecular sieve porous layer open tubular column.

Considering the severe constraints of space instrumentation, a great improvement for the in situ gas chromatographic (GC) determination of permanent and noble gases in a cometary nucleus is the use of a new carbon molecular sieve porous layer open tubular (PLOT) column called Carbobond. No exhaustive data dealing with this column being available, studies were carried out to entirely characterize its analytical performances, especially when used under the operating conditions of the cometary sampling and composition (COSAC) experiment of the European Space Agency (ESA) Rosetta space mission to be launched in 2003 for a rendezvous with comet 46 P/Wirtanen in 2011. The high efficiency and speed of analysis of this column at both atmospheric and vacuum outlet column pressure is demonstrated, and the kinetic mass transfer contribution of this carbon molecular sieve adsorbent is calculated. Besides, differential adsorption enthalpies of several gases and light hydrocarbons were determined from the variation of retention volume with temperature. The data indicate close adsorption behaviors on the Carbobond porous layer adsorbent and on the carbon molecular sieve Carboxen support used to prepare the packed columns. Moreover, taking into account the in situ operating conditions of the experiment, a study of two columns with different porous layer thicknesses allowed one to optimize the separation of the target components and to select the column parameters compatible with the instrument constraints. Comparison with columns of similar selectivity shows that these capillary columns are the first ones able to perform the same work as the packed and micro-packed columns dedicated to the separation of this range of compounds in GC space exploration.

Gas chromatography for in situ analysis of a cometary nucleus III. Multi-capillary column system for the cometary sampling and composition experiment of the Rosetta lander probe

The cometary sampling and composition (COSAC) experiment is one of the principal experiments of the surface lander probe of the European Space Agency Rosetta mission to be launched in January 2003. The instrument is designed for the in situ chemical analysis of a cometary nucleus as the details of the nucleus composition are of primary importance for understanding both the formation of the solar system, and the origin of life on Earth. The COSAC experiment consists of an evaporation/pyrolysis device and two analytical systems: a multi-column gas chromatograph and a high-resolution time-of-flight mass spectrometer which may either be operated alone or in a coupled mode. The gas chromatograph includes five general purpose chromatographic columns and three chiral ones, all mounted in parallel. Taking into account the chemical species potentially present in the cometary nucleus as well as the space constraints, a set of five complementary columns was selected to perform the separation and identification of the compounds present in the cometary nucleus. This set of columns includes a carbon molecular sieve porous-layer open tubular (PLOT) column used for the separation of both the noble and other permanent gases, and the C1-C2 hydrocarbons. A second PLOT column uses a divinylbenzene-ethylene glycol-dimethylacrylate porous polymer as stationary phase for the analysis of a wide range of C1-C2 organic molecules, Two complementary wall-coated open tubular (WCOT) columns with polydimethylsiloxane (PDMS) liquid stationary phases, one containing cyanopropyl-phenylsiloxane and the other diphenylsiloxane groups, are designed to target the same range of organic compounds (C3-C7) which could be representative of the widest range of cometary compounds. A third WCOT column with an apolar stationary phase made of non-substituted PDMS is used for the separation and identification of higher-molecular-mass compounds (up to C10) and aromatic species (monoaromatic and polyaromatic). This paper describes these five general-purpose capillary PLOT and WCOT columns, selected to be used in the COSAC GC system. The analytical capabilities are examined with a special emphasis on the exobiological and planetological implications.

Gas chromatography for in situ analysis of a cometary nucleus: characterization and optimization of diphenyl / dimethylpolysiloxane stationary phases

The development of a gas chromatograph for the cometary sampling and composition (COSAC) experiment is described in the context of the preparation for the European Space Agency (ESA) Mission Rosetta for investigation of a cometary nucleus. COSAC is one out of ten experiments on the Rosetta Lander. Its scientific goal is to analyze in situ the chemical composition of the volatile constituents of the nucleus of the target comet P/Wirtanen. Constituted of several (up to eight) capillary wall-coated and porous-layer open tubular columns operating in parallel, the GC system is designed to separate and identify both organic and inorganic compounds which evolve from the comet naturally or are obtained from cometary samples through stepwise heating in a miniaturized pyrolizer. In this first part of our study, dimethylpolysiloxane (DMPS) stationary phases with increasing percentages of diphenyl substituted group (DP) have been investigated. A coupled experimental and theoretical approach has been taken in order to predict chromatographic data. By the use of a four-point experimental calibration (0 to 65% diphenyl group) in conjunction with Pro ezGC modeling software, results in prediction of multicomponent chromatograms with a mean error less than 5% for each compound retention time were obtained, irrespective of the stationary phases diphenyl content and column physical parameters. The possibility to associate such phases is illustrated by the evolution of coelutions obtained on a non-polar (100% DMPS) and a medium polar (65% DP-DMPS) stationary phase, respectively. This study showed that with a small number of well tuned DP-DMPS columns, the separation and identification of most of the targeted compounds can be achieved with a minimum amount of coelutions and within the experiment requirements.

Gas chromatography for in situ analysis of a cometary nucleus - IV. Study of capillary column robustness for space application

As part of the development of the European Space Agency Rosetta space mission to investigate a cometary nucleus, the selection of columns dedicated to the gas chromatographic subsystem of the Cometary Sampling and Composition (COSAC) experiment was achieved. Once the space probe launched, these columns will be exposed to the harsh environmental constraints of space missions: vibrations, radiation (by photons or energetic particles), space vacuum, and large temperature range. In order to test the resistance of the flight columns and their stationary phases, the columns were exposed to these rough conditions reproduced in the laboratory. The comparison of the analytical performances of the columns, evaluated prior and after the environmental tests, demonstrated that all the columns withstand space constraints, and that their analytical properties were preserved. Therefore, all the selected capillary columns, even having porous layer or chiral stationary phases, were qualified for space exploration.