Nitrogen isotopic fractionation during plasma synthesis of Titan's aerosols analogues

The Cassini-Huygens mission recently provided measurements of the abundance of nitrogen isotopes in Titan's atmosphere. The 14N/15N ratio in the two most abundant N-bearing molecules in Titan's atmosphere was found to be 183×5 for N2 [1] and 56×8 for HCN [2]. Those two molecules are greatly enriched in the heavier isotope 15N compared to our terrestrial atmosphere and Titan's HCN is about three times richer in 15N than its potential photochemical precursor N2. This implies an important fractionation process in the HCN production chain, which is tentatively attributed to an isotopic selectivity of the photodissociation of N2 in Titan's ionosphere [3-4]. The organic aerosols, forming the Titan's orange characteristic haze layers, also contain large amounts of nitrogen [5], and thus represent a third important nitrogen reservoir in Titan's atmosphere. These organic aerosols are presumably produced in the upper atmosphere by chemical reactions between N2 and CH4 induced by solar radiation and electron bombardment from Saturn's magnetosphere. As HCN is a possible precursor for aerosol polymerization [6-7], the 15N enrichment observed in HCN may be linked to the polymerization process. Unfortunately, no data exists on the isotopic nitrogen abundance in Titan's aerosols, and this question remains open. To address this issue, laboratory aerosols analogues have been produced in a N2-CH4 plasma and their nitrogen isotopic composition have been investigated. In this study, the experimental aerosols, called " tholins ", have been synthetized in the PAMPRE reactor (LATMOS, France). This setup is dedicated to simulate chemical processes occurring in Titan's atmosphere and consists in an RF plasma discharge initiated in a N2-CH4 gas mixture at room temperature [8-9]. For our purpose, tholins were produced at different initial CH4 percentages (1, 2, 5, 10%), representative of the variation of the CH4 concentration in Titan's atmosphere. 15N/14N ratio of the N2 gas used in the initial gas mixture was analyzed by dual-inlet and tholins nitrogen isotopes were measured by EA-IRMS. PAMPRE tholins are depleted in 15N by -15 to -25‰ relative to the initial N2. Comparison of this nitrogen isotopic fractionation with a N2-CO-H2O plasma experiment done in very similar experimental conditions and resulting in a very close 15N depletion, has led us to interpret this 15N depletion between N2 and organic aerosols as a kinetic isotopic fractionation occurring during N2 dissociation in the plasma. This nitrogen isotopic fractionation, although important and larger than what is observed in natural terrestrial samples, is weak compared to what is measured in Titan's atmosphere for N2 and HCN. This apparent inconsistency will be discussed. [1] Niemann et al. (2010) JGR, 115, 1151-1154. [2] Vinatier et al. (2007) Icarus, 191, 712-721. [3] Liang et al. (2007) Ap.J. Lett., 664, L115. [4] Croteau et al. (2011) Ap.J. Lett., 728, L32. [5] Israel et al. (2005) [6] Lebonnois et al. (2002) Icarus, 159, 505-517. [7] Lavvas et al. 2008) Planet. Space Sci., 56, 67-99. [8] Szopa et al. (2006) Planet. Space. Sci., 54, 394-404. [9] Sciamma-O'Brien et al. (2010) Icarus, 209, 704-714