Search

To study Titan, the largest moon of Saturn, laboratory simulation experiments have been performed to obtain analogues of Titan's aerosols (named tholins) using different energy sources. Tholins, which have been demonstrated to represent aerosols in Titan's haze layers, are a complex mixture, resulting from the chemical evolution of several hydrocarbons and nitriles. Their chromatographic analysis yields complex chromatograms, which require the use of mathematical procedures to extract from them all the information they contain. Two different chemometric approaches (the Fourier analysis approach and the statistical model of peak overlapping) have been successfully applied to pyrolysis-GC-MS chromatogram of a tholin sample. Fundamental information on the mixture's chemical composition (number of components, m) and on the separation system performance (separation efficiency, sigma) can be easily estimated: the excellent correspondence between the data calculated by the two independent procedures proves the reliability of the statistical approaches in characterizing a tholin chromatogram. Moreover, the plot of autocorrelation function contains, in a simplified form, all the information on the retention pattern: retention recursivities can be easily singled out and related to specific molecular structure variations. Therefore, the autocorrelation function (ACF) plot constitutes a simplified fingerprint of the pyrolysis products of tholins, which can be used as a powerful tool to characterize a tholin sample.

Aerosols in Titan's 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 Titan's 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. [ABSTRACT FROM AUTHOR]

Biemann calls into question our preliminary interpretations of our experimental results. A comparison of laboratory and flight measurements should settle the uncertainties he raises. In addition to evaluating instrumental characteristics such as the 'piston effect', a technique we used for injecting oven-gas content for gas chromatography–mass spectrometry (GC–MS), such studies should enable a wide range of possible compositions for Titan's aerosols to be investigated. Our aerosol collection and pyrolysis (ACP) measurements in Titan's atmosphere can then be revisited. [ABSTRACT FROM AUTHOR]

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

Abstract: This work deals with the optical constant characterization of Titan aerosol analogues or “tholins” produced with the PAMPRE experimental setup and deposited as thin films onto a silicon substrate. Tholins were produced in different N2–CH4 gaseous mixtures to study the effect of the initial methane concentration on their optical constants. The real (n) and imaginary (k) parts of the complex refractive index were determined using the spectroscopic ellipsometry technique in the 370–1000nm wavelength range. We found that optical constants depend strongly on the methane concentrations of the gas phase in which tholins are produced: imaginary optical index (k) decreases with initial CH4 concentration from 2.3×10−2 down to 2.7×10−3 at 1000nm wavelength, while the real optical index (n) increases from 1.48 up to 1.58 at 1000nm wavelength. The larger absorption in the visible range of tholins produced at lower methane percentage is explained by an increase of the secondary and primary amines signature in the mid-IR absorption. Comparison with results of other tholins and data from Titan observations are presented. We found an agreement between our values obtained with 10% methane concentration, and Imanaka et al. (Imanaka, H., Khare, B.N., Elsila, J.E., Bakes, E.L.O., McKay, C.P., Cruikshank, D.P., Sugita, S., Matsui, T., Zare, R.N. [2004]. Icarus, 168, 344–366) values, in spite of the difference in the analytical method. This confirms a reliability of the optical properties of tholins prepared with various setups but with similar plasma conditions. Our comparison with Titan’s observations also raises a possible inconsistency between the mid-IR aerosol signature by VIMS and CIRS Cassini instruments and the visible Huygens-DISR derived data. The mid-IR VIMS and CIRS signatures are in agreement with an aerosol dominated by an aliphatic carbon content, whereas the important visible absorption derived from the DISR measurement seems to be incompatible with such an important aliphatic content, but more compatible with an amine-rich aerosol. [Copyright &y& Elsevier]

Abstract: The chemistry leading to the formation of solid aerosols (tholins) in Titan''s atmosphere is simulated by a capacitively coupled plasma in a N2–CH4 gas mixture. The solid grains are produced in volume directly in the gas phase and studied ex-situ by SEM imaging and by light scattering on clouds of particles. The scattered light properties depend on the physical properties of the particles (morphologies, size distribution), as well as on the phase angle and the wavelength of the light. The particles may be aggregated or agglomerated grains. The grains size distribution is studied as a function of plasma parameters such as initial methane concentration introduced into the discharge, gas flow, absorbed RF power and plasma duration. The average grain size increases when the amount of CH4 increases, when the gas flow decreases, and when the plasma duration increases up to a limit for each production condition. For all the samples, the absorption decreases with increasing wavelength in the visible domain. As usually found for irregular particles, the polarization phase curves have a bell-shaped positive branch and a shallow negative branch. The maximum of polarization (P max) increases when the average grain size decreases (sub-μm-sized grains). To obtain P max values within the range of those measured in Titan''s atmosphere; the average grains diameter has to be smaller than 100nm, in agreement with the space observations results. In the light-scattering experiment, the size of the agglomerates in the clouds is in the 40–80μm range in equivalent diameter. As a consequence P max increases with decreasing wavelength due to the increasing absorption, in agreement with observations of Titan from outside the atmosphere. [Copyright &y& Elsevier]

Abstract: Since the discovery of the main composition of Titan''s atmosphere, many laboratory experiments have been carried out to reproduce its chemical evolution, particularly the formation of organic haze particles found throughout this atmosphere. Some of these simulations have produced solid products—referred to as Titan''s tholins—that are assumed to have properties similar to those of Titan''s aerosols. In the present work, we focus on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan''s tholins. Initial 12C/13C isotopic ratios measured on tholins made in the laboratory using cold plasma discharges are presented. Measurements of isotopic enhancement in 13C (δ 13C), both on tholins and on the initial gas mixture (N2:CH4 (98:2)) used to produce them do not show any clear deficit or enrichment in 13C relative to 12C in the lab-made tholins compared to the initial gas mixture. Preliminary data recovered from the Aerosol Collector Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan''s aerosols may also be exempt of carbon isotopic enrichment. This observation creates possibilities for deeper analysis of ACP experiment data. [Copyright &y& Elsevier]