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Although the Cassini Spacecraft and the Huygens lander provided numerousinformation about Titan atmospheric chemistry and the formation of itsaerosols, the exact composition of these aerosols still remains unknown. Afruitful proxy to investigate these aerosols is the use of laboratoryexperiments that allow producing and studying analogs of Titan aerosol, theso35 called tholins. Even when produced in the laboratory, unveiling the exactcomposition of the aerosol remains problematic due to the high complexity ofthe material. Numerous advances have been recently made using high-resolutionmass spectrometry (HRMS) (Pernot et al. 2010, Somogyi et al. 2012, Gautier etal. 2014) that allowed the separation of isobaric compounds and a robustidentification of chemical species composing tholins regarding their molecularformulae. Nevertheless isomeric species cannot be resolved by a simple massmeasurement. We propose here an analysis of tholins by high performance liquidchromatography (HPLC) coupled to HRMS to unveil this isomeric ambiguity forsome of the major tholins compounds. By comparing chromatograms obtained whenanalyzing tholins and chemical standards, we strictly identified sevenmolecules in our tholins samples: melamine, cyanoguanidine,6-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-triaminopyrimidine, 3-amino-1,2,4-triazole, 3,5-Dimethyl-1,2,4-triazole and 2,4-diamino-1,3,5-triazine.Several molecules, including hexamethylenetriamine (HMT) were not present atdetectable levels in our sample. The use for the first time of a coupledHPLC-HRMS technique applied to tholins study demonstrated the interest of sucha technique compared to single high-resolution mass spectrometry for the studyof tholins composition.

Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments