Noble gases, nitrogen, and methane from the deep interior to the atmosphere of Titan

Titan's thick N-2-CH4 atmosphere is unlike any in the Solar System, and its origin has been shrouded in mystery for over half a century. Here, I perform a detailed analysis of chemical and isotopic data from the Cassini-Huygens mission to develop the hypothesis that Titan's (non-photochemical) atmospheric gases came from deep within. It is suggested that Titan's CH4, N-2, and noble gases originated in a rocky core buried inside the giant satellite, and hydrothermal and cryovolcanic processes were critical to the creation of Titan's atmosphere. Mass balance and chemical equilibrium calculations demonstrate that all aspects of this hypothesis can be considered geochemically plausible with respect to contemporary observational, experimental, and theoretical knowledge. Specifically, I show that a rocky core with a bulk noble gas content similar to that in CI carbonaceous meteorites would contain sufficient Ar-36 and Ne-22 to explain their reported abundances. I also show that Henry's law constants for noble gases in relevant condensed phases can be correlated with the size of their atoms, which leads to expected mixing ratios for 84Ki. (-0.2 ppbv) and 132Xe (-0.01 ppbv) that can explain why these species have yet to be detected (Huygens upper limit <10 ppbv). The outgassing of volatiles into Titan's atmosphere may be restricted by the stability of clathrate hydrates in Titan's interior. The noble gas geochemistry also provides significant new insights into the origin of Ny and CH4 on Titan, as I find that Ar and Ny, and Kr and CH4 should exhibit similar phase partitioning behavior on Titan. One implication is that over 95% of Titan's Ny may still reside in the interior. Another key result is that the upper limit from the Huygens GC-MS on the Kr/CH4 ratio in Titan's atmosphere is far too low to be consistent with accretion of primordial CH4 clathrate, which motivates me to consider endogenic production of CH4 from CO2 as a result of geochemical reactions between liquid water and anhydrous rock (i.e., serpentinization). I show that sufficient CH4 can be produced to replenish Titan's atmosphere many times over in the face of irreversible photolysis and escape of CH4, which is consistent with the favored model of episodic cryovolcanic outgassing. There should also have been enough NH3 inside Titan so that its thermal decomposition in a hot rocky core can generate the observed atmospheric Ny, and if correct this model would imply that Titan's interior has experienced vigorous hydrothermal processing. The similarity in N-14/N-16 between cometary NH3 and Titan's Ny is consistent with this picture. As for the isotopes in CH4, I show that their observed relative abundances can be explained by low-temperature (similar to 20 degrees C) equilibria with liquid water (D/H) and the expected aqueous alteration mineral calcite (C-12/C-13), provided that nickel was present to catalyze isotopic exchange over geologic timescales. The present hypothesis is chemically and isotopically consistent with the Cassini-Huygens data, and it implies that the formation of Titan's atmosphere would have been an unavoidable consequence of volatile processing that was driven by the geophysical evolution of the interior. If all of the atmospheric N-2 and CH4 have an endogenic origin, then no more than 1. 6 times the present amount of N-2 can be lost by photochemistry and escape over the history of the atmosphere; and the D/H ratio in Titan's water should be much lower than that in Enceladus' plume. Given its important implications to the origin and evolution of volatiles in the outer Solar System, we must go back to Titan to acquire additional isotopic data that will allow more rigorous tests of models of the origin of its atmosphere. I predict the following isotopic ratios: Ne-26/Ne-22 8.9 approximate to Ar-36/Ar-38 as 5.3, (N-14/N-15)NH3 as 130-170, (C-12/C-13)(CO2) 84, (D/H)H(2)o approximate to 1.7 x 10(-4); and recommend that future in situ instrumentation have the capability to measure the rare isotopologues of N-2 and CH4, which represent previously unconsidered but potentially valuable sources of geochemical information on the origin and evolution of Titan's atmosphere. (C) 2015 Elsevier Inc. All rights reserved.