Titan's methane clock

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Scientific paper

Measurements of the 12C/13C and D/H isotopic ratios in Titan's methane show intriguing differences from the values recorded in the giant planets. This implies that either (1) the atmosphere was differently endowed with material at the time of formation, or (2) evolutionary processes are at work in the moon's atmosphere - or some combination of the two.
The Huygens Gas Chromatograph Mass Spectrometer Instrument (GCMS) found 12CH4/13CH4 = 82 +/- 1 (Niemann et al. 2005), some 7% lower than the giant planets' value of 88 +/- 7 (Sada et al. 1996), which closely matches the terrestrial inorganic standard of 89. The Cassini Composite Infrared Spectrometer (CIRS) has previously reported 12CH4/13CH4 of 77 +/-3 based on nadir sounding, which we now revise upwards to 80 +/- 4 based on more accurate limb sounding. The CIRS and GCMS results are therefore in agreement about an overall enrichment in 13CH4 of ~10%.
The value of D/H in Titan's CH4 has long been controversial: historical measurements have ranged from about 8-15 x 10-5 (e.g. Coustenis et al. 1989, Coustenis et al. 2003). A recent measurement based on CIRS limb data by Bezard et al. (2007) puts the D/H in CH4 at (13 +/- 1) x 10-5, very much greater than in Jupiter and Saturn, ~2 x 10-5 (Mahaffy et al. 1998, Fletcher et al. 2009).
To add complexity, the 12C/13C and D/H vary among molecules in Titan atmosphere, typically showing enhancement in D but depletion in 13C in the daughter species (H2, C2H2, C2H6), relative to the photochemical progenitor, methane. Jennings et al. (2009) have sought to interpret the variance in carbon isotopes as a Kinetic Isotope Effect (KIE), whilst an explanation for the D/H in all molecules remains elusive (Cordier et al. 2008). In this presentation we argue that evolution of isotopic ratios in Titan's methane over time forms a ticking 'clock', somewhat analogous to isotopic ratios in geochronology. Under plausible assumptions about the initial values and subsequent replenishment, various ages for atmosphere may be inferred, constraining Titan's possible histories.

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