Nitrogen incorporation in Titanʹs tholins inferred by high resolution orbitrap mass spectrometry and gas chromatography–mass spectrometry

Influx of solar photons and heavy charged particles from Saturnʹs magnetosphere on Titanʹs atmosphere – mainly comprised of methane and nitrogen – induce an intense organic photochemistry which leads to the formation of a large amount of aerosols in suspension in the atmosphere. In order to infer the role of nitrogen in aerosol formation processes we produced laboratory analogs of Titanʹs aerosols. In this work, we compare the composition of different analogs by using high resolution mass spectrometry and propose an additional study using gas-chromatography coupled to mass-spectrometry for a new kind of analog produced by polymerization of cryogenically trapped gaseous neutral species. The comparison of these materials emphasizes the importance of ion chemistry processes for the inclusion of nitrogen in molecules constituting Titanʹs tholins. A statistical approach is also used for the treatment of high resolution mass spectra of these highly complex organic materials. This method allows distinguishing molecular families that can be reconstructed by an ideal copolymer. We investigate several copolymer reconstructions, and we suggest that an HCN (or CH3CN)/C2H4 based copolymer agrees well with the polymeric structure of tholins produced with 5% of methane in nitrogen.