Investigating the Vertical Variability of Titan’s 14N/15N in HCN
(2025)
Authors:
Alexander Thelen, Katherine de Kleer, Nicholas Teanby, Amy Hofmann, Martin Cordiner, Conor Nixon, Jonathon Nosowitz, Patrick Irwin
Abstract:
Titan’s substantial atmosphere is primarily composed of molecular nitrogen (N2) and methane (CH4), which are dissociated by solar UV photons and subsequently generate a vast chemical network of trace gases. The composition of Titan’s atmosphere is markedly different than that of Saturn, including both the complex molecular inventory and the hitherto measured isotopic ratios – including that of nitrogen (14N/15N). Atmospheric and interior evolution models (e.g., Mandt et al., 2014) indicate that the atmospheres of Saturn and Titan did not form in the same manner or from the same constituents, and that Titan’s atmospheric N2 may have originated from its interior as NH3. The evolution of 14N/15N in Titan’s atmosphere over time does not result in a value comparable to that measured on Saturn and instead is closer to cometary values; this indicates that the origin of Titan’s atmosphere appears to be from protosolar planetesimals enriched in ammonia and not from the sub-Saturnian nebula. However, selective isotopic fractionation of molecular species in Titan’s atmosphere complicates this picture, as the isotopic ratios may vary as a function of altitude (Figure 1). To further constrain the evolution of Titan’s atmosphere – and indeed, its origin – isotopic ratios must be measured throughout its atmosphere, instead of being interpreted from bulk values likely only representative of the stratosphere.While the measurement of Titan’s 14N/15N in N2 (167.7; Niemann et al. 2010) places it firmly below the lower limit derived for Saturn (~350; Fletcher et al., 2014), Titan’s atmospheric nitriles (e.g., HCN, HC3N, CH3CN) are further enriched in 15N, resulting in ratios closer to 70 (Molter et al., 2016; Cordiner et al., 2018; Nosowitz et al., 2025). The variation in nitrogen isotopic ratios between the nitriles and N2 is thought to be the result of higher photolytic efficiency of 15N14N compared to N2 in the upper atmosphere (~900 km), resulting in increased 15N incorporated into nitrogen-bearing species (Liang et al., 2007; Dobrijevic & Loison, 2018; Vuitton et al., 2019). As these species are advected to lower altitudes, the nitrogen isotope ratio may vary vertically (Figure 1, red and black profiles), but previous measurements have only presented bulk atmospheric isotope ratios primarily representing Titan’s stratosphere (Figure 1, blue lines).Recent observations with the Atacama Large Millimeter/submillimeter Array (ALMA) have allowed for the derivation of vertical abundance profiles of Titan’s trace atmospheric species and measurements of N, D, and O-bearing isotopologues (Molter et al., 2016; Serigano et al., 2016; Cordiner et al., 2018; Thelen et al., 2019; Nosowitz et al., 2025). However, vertical isotopic ratio profiles have yet to be derived. Here, we utilize observations acquired with ALMA in July 2022 containing high sensitivity measurements of the HC15N J=4–3 transition at 344.2 GHz (~ 0.87 mm) to investigate vertical variations in the 14N/15N of Titan’s HCN. We compare the results of the vertical 14N/15N profile to those predicted by photochemical models to determine the impact of the isotopic-selective photodissociation of nitrogen-bearing molecular species in Titan’s atmosphere, and the impact of the Saturnian and space environments that vary between model implementations.Figure 1. 14N/15N profile for HCN predicted by photochemical models from Vuitton et al. (2019; black line) and Dobrijevic & Loison (2018; red line). Blue colored bars in the lower atmosphere represent previous HCN nitrogen isotope ratios from Cassini, Herschel, and ground-based (sub)millimeter observations (see Molter et al., 2016, and references therein). Measurements are offset vertically for clarity, and all refer to HC14N/HC15N measurements for the bulk stratosphere.References:Cordiner et al., 2018, The Astrophysical Journal Letters, 859, L15.Dobrijevic & Loison, 2018, Icarus, 307, 371.Fletcher et al., 2014, Icarus, 238, 170.Liang et al., 2007, The Astrophysical Journal Letters, 644, L115.Mandt et al. 2014, The Astrophysical Journal Letters, 788, L24.Molter et al., 2016, The Astronomical Journal, 152, 42.Niemann et al., 2010, Journal of Geophysical Research, 115, E12006.Nosowitz et al., 2025, The Planetary Science Journal, 6, 107.Serigano et al., 2016, The Astrophysical Journal Letters, 821, L8.Thelen et al., 2019, The Astronomical Journal, 157, 219.Vuitton et al., 2019, Icarus, 324, 120.