13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

• Photochemical irradiation of CH4/N2 atmospheres fractionates C and N isotopes.
• This is the first study of photochemical fractionation during aerosol formation.
• Photochemical aerosol analogs of Titan haze were enriched in C-13 and N-14.
• Isotopic fractionation and N/C ratio are dependent on methane concentration.

The ratios of the stable isotopes that comprise each chemical species in Titan’s atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation – organic aerosol formation and subsequent deposition onto the surface of Titan – has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as ‘tholins’, via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.