SEASONAL EVOLUTION OF TITAN'S STRATOSPHERE NEAR THE POLES.

In this paper we report the monitoring of seasonal evolution near Titan's poles. We find Titan's south pole to exhibit since 2010 a strong temperature decrease and a dramatic enhancement of several trace species such as complex hydrocarbons and nitriles (HC3N and C6H6 in particular) previously only observed at high northern latitudes (Coustenis et al. 2016 and references therein). This results from the seasonal change on Titan going from winter (2002) to summer (2017) in the north and, at the same time, the onset of winter in the south pole. During this transition period atmospheric components with longer chemical lifetimes linger in the north undergoing slow photochemical destruction, while those with shorter lifetimes decrease and reappear in the south. An opposite effect was expected in the north, but not observed with certainty until now. We present here an analysis of high-resolution nadir spectra acquired by Cassini/CIRS at in the past years and describe the temperature and composition variations near Titan's poles. From 2013 until 2016, the northern polar region has shown a temperature increase of 10 K, while the south has shown a more significant decrease (up to 25 K) in a similar period of time. While the south polar region is continuously enhanced since about 2012, the chemical content in the north is finally showing a clear depletion for most molecules only since 2015. This is indicative of a non-symmetrical response to the seasons in Titan's stratosphere that can set constraints on photochemical and GCM models.

Formation of NH3 and CH2NH in Titan's upper atmosphere.

The large abundance of NH3 in Titan's upper atmosphere is a consequence of coupled ion and neutral chemistry. The density of NH3 is inferred from the measured abundance of NH4+. NH3 is produced primarily through reaction of NH2 with H2CN, a process neglected in previous models. NH2 is produced by several reactions including electron recombination of CH2NH2+. The density of CH2NH2+ is closely linked to the density of CH2NH through proton exchange reactions and recombination. CH2NH is produced by reaction of N(2D) and NH with ambient hydrocarbons. Thus, production of NH3 is the result of a chain of reactions involving non-nitrile functional groups and the large density of NH3 implies large densities for these associated molecules. This suggests that amine and imine functional groups may be incorporated as well in other, more complex organic molecules.

Composition and chemistry of Titan's thermosphere and ionosphere.

Titan has long been known to harbour the richest atmospheric chemistry in the Solar System. Until recently, it had been believed that complex hydrocarbons and nitriles were produced through neutral chemistry that would eventually lead to the formation of micrometre sized organic aerosols. However, recent measurements by the Cassini spacecraft are drastically changing our understanding of Titan's chemistry. The Ion and Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) revealed an extraordinary complex ionospheric composition. INMS detected roughly 50 positive ions with m/z<100 and a density higher than 0.1cm-3. CAPS provided evidence for heavy (up to 350amu) positively and negatively charged (up to 4000amu) ions. These observations all indicate that Titan's ionospheric chemistry is incredibly complex and that molecular growth starts in the upper atmosphere rather than at lower altitude. Here, we review the recent progress made on ionospheric chemistry. The presence of heavy neutrals in the upper atmosphere has been inferred as a direct consequence of the presence of complex positive ions. Benzene (C6H6) is created by ion chemistry at high altitudes and its main photolysis product, the phenyl radical (C6H5), is at the origin of the formation of aromatic species at lower altitude.