Prof. Patrick Irwin

Abstract:

Abstract Curiously, n-butane has yet to be detected at Titan, though it is predicted to be present in a wide range of abundances that span over 2.5 orders of magnitude. We have searched infrared spectroscopic observations of Titan for signals from n-butane (n-C4H10) in Titan’s stratosphere. Three sets of Cassini Composite Infrared Spectrometer Focal Plane 4 (1050–1500 cm−1) observations were selected for modeling, having been collected from different flybys and pointing latitudes. We modeled the observations with the Nonlinear Optimal Estimator for MultivariatE Spectral AnalySIS radiative transfer tool. Temperature profiles were retrieved for each of the data sets by modeling the ν 4 emission from methane near 1305 cm−1. Then, incorporating the temperature profiles, we retrieved abundances of all of Titan’s known trace gases that are active in this spectral region, reliably reproducing the observations. We then systematically tested a set of models with varying abundances of n-butane, investigating how the addition of this gas affected the fits. We did this for several different photochemically predicted abundance profiles from the literature, as well as for a constant-with-altitude profile. Ultimately, though we did not produce any firm detection of n-butane, we derived new upper limits on its abundance specific to the use of each profile and to multiple different ranges of stratospheric altitudes. These results will tightly constrain the C4 chemistry of future photochemical modeling of Titan’s atmosphere and also motivate the continued search for n-butane and its isomer, isobutane.

Abstract:

Isotopic ratios in atmospheric CO2 are shaped by various processes throughout Mars' history, and can help understand what the atmosphere of early Mars was like to sustain liquid water on its surface. In this study, we monitor the O and C isotopic composition of CO2 between 70 and 130 km for more than half a Martian year using solar occultation observations by the Atmospheric Chemistry Suite onboard the ExoMars Trace Gas Orbiter. We find the vertical trends of the isotopic ratios to be consistent with the expectations from diffusive separation above the homopause, with average values below this altitude being consistent with Earth-like fractionation (δ13C = −3 ± 37‰; δ18O = −29 ± 38‰; and δ17O = −11 ± 41‰). Using these measurements, we estimate that at least 20%–40% of primordial C on Mars has escaped to space throughout history. The total amount of C lost from the atmosphere is likely to be well in excess of this lower limit, due to carbonate formation and further sink processes. In addition, we propose a photochemical transfer of light O from H2O to CO2 to explain the larger enrichment in the 18O/16O ratio in H2O than in CO2.