Laboratory investigations of Titan haze formation: In situ measurement of gas and particle composition

Abstract Prior to the arrival of the Cassini-Huygens spacecraft, aerosol production in Titan’s atmosphere was believed to begin in the stratosphere where chemical processes are predominantly initiated by far ultraviolet (FUV) radiation. However, measurements taken by the Cassini Ultraviolet Imaging Spectrograph (UVIS) and Cassini Plasma Spectrometer (CAPS) indicate that haze formation initiates in the thermosphere where there is a greater flux of extreme ultraviolet (EUV) photons and energetic particles available to initiate chemical reactions, including the destruction of N 2 . The discovery of previously unpredicted nitrogen species in measurements of Titan’s atmosphere by the Cassini Ion and Neutral Mass Spectrometer (INMS) indicates that nitrogen participates in the chemistry to a much greater extent than was appreciated before Cassini. The degree of nitrogen incorporation in the haze particles is important for understanding the diversity of molecules that may be present in Titan’s atmosphere and on its surface. We have conducted a series of Titan atmosphere simulation experiments using either spark discharge (Tesla coil) or FUV photons (deuterium lamp) to initiate chemistry in CH 4 /N 2 gas mixtures ranging from 0.01% CH 4 /99.99% N 2 to 10% CH 4 /90% N 2 . We obtained in situ real-time measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) to measure the particle composition as a function of particle size and a proton-transfer ion-trap mass spectrometer (PIT-MS) to measure the composition of gas phase products. These two techniques allow us to investigate the effect of energy source and initial CH 4 concentration on the degree of nitrogen incorporation in both the gas and solid phase products. The results presented here confirm that FUV photons produce not only solid phase nitrogen bearing products but also gas phase nitrogen species. We find that in both the gas and solid phase, nitrogen is found in nitriles rather than amines and that both the gas phase and solid phase products are composed primarily of molecules with a low degree of aromaticity. The UV experiments reproduce the absolute abundances measured in Titan’s stratosphere for a number of gas phase species including C 4 H 2 , C 6 H 6 , HCN, CH 3 CN, HC 3 N, and C 2 H 5 CN.