On the H2 abundance and ortho-to-para ratio in Titan's troposphere

Abstract

We have analyzed spectra recorded between 50 and 650 cm−1 by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft at low and high emission angles to determine simultaneously the H2 mole fraction and ortho-to-para ratio in Titan's troposphere. We used constraints from limb spectra between 50 and 900 cm−1 and from in situ measurements by the Huygens probe to characterize the temperature, haze and gaseous absorber profiles. We confirm that the N2-CH4 collision-induced absorption (CIA) coefficients used up to now need to be increased by about 52% at temperatures of 70–85 K. We find that the N2-N2 CIA coefficients are also too low in the N2 band far wing, beyond 110 cm−1, in agreement with recent quantum mechanical calculations. We derived a H2 mole fraction equal to (0.88 ± 0.13) × 10−3, which pertains to the ~1–34 km altitude range probed by the S0(0) and S0(1) lines. This result agrees with a previous determination based only on the H2-N2 dimer transition in the S0(0) line, and with the in situ measurement by the Gas Chromatograph Mass Spectrometer (GCMS) aboard Huygens. It is 3–4 times smaller than the value measured in situ by the Ion Neutral Mass Spectrometer (INMS) of Cassini at 1000–1100 km. The H2 para fraction is close to equilibrium in the 20-km region. CIRS spectra can be fitted assuming ortho-to-para (o-p) H2 thermodynamical equilibrium at all levels or a constant para fraction in the range 0.49–0.53. We have investigated different mechanisms that may operate in Titan's atmosphere to equilibrate the H2 o-p ratio and we have developed a one-dimensional model that solves the continuity equation in presence of such conversion mechanisms. We conclude that exchange with H atoms in the gas phase or magnetic interaction of H2 in a physisorbed state on the surface of aerosols are too slow compared with atmospheric mixing to play a significant role. On the other hand, magnetic interaction of H2 with CH4, and to a lesser extent N2, can operate on a timescale similar to the vertical mixing time in the troposphere. This process is thus likely responsible for the o-p equilibration of H2 in the mid-troposphere implied by CIRS measurements. The model can reproduce the inferred o-p ratio in the 20-km region, assuming low atmospheric mixing in the troposphere down to 15–20 km and conversion rates with CH4 or N2 slightly larger than obtained from an extrapolation of natural ortho-para conversion rate measured in gaseous hydrogen.