In this chapter we describe the remote sensing measurement of nitrogen-bearing species in Titans atmosphere by the Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft. This instrument, which detects the thermal infrared spectrum from 10-
1500 cm-1 (1000-7 microns) is sensitive to vibrational emissions of gases and condensates in Titans stratosphere and lower mesosphere, permitting the measurement of ambient temperature and the abundances of gases and particulates. Three N-bearing species are firmly detected: HCN, HC3N and C2N2, and their vertical and latitudinal distributions have been mapped. In addition, ices of HC3N and possibly C4N2 are also seen in the far-infrared spectrum at high latitudes during the northern winter. The HC(15)N isotopologue has been measured, permitting the inference of the 14N/15N ratio in this species, which differs markedly (lower) than in the bulk nitrogen reservoir (N2). We also describe the search in the CIRS spectrum, and inferred upper limits, for NH3 and CH3CN. CIRS is now observing seasonal transition on Titan and the gas abundance distributions are changing accordingly, acting as tracers of the changing atmospheric circulation. The prospects for further CIRS science in the remaining five years of the Cassini mission are discussed.
We have searched for the presence of simple P and S-bearing molecules in Titans atmosphere, by looking for the characteristic signatures of phosphine and hydrogen sulfide in infrared spectra obtained by Cassini CIRS. As a result we have placed the fi
rst upper limits on the stratospheric abundances, which are 1 ppb (PH3) and 330 ppb (H2S), at the 2-sigma significance level.
In this paper we describe a first quantitative search for several molecules in Titans stratosphere in Cassini CIRS infrared spectra. These are: ammonia (NH3), methanol (CH3OH), formaldehyde (H2CO), and acetonitrile (CH3CN), all of which are predicted
by photochemical models but only the last of which observed, and not in the infrared. We find non-detections in all cases, but derive upper limits on the abundances from low-noise observations at 25{deg}S and 75{deg}N. Comparing these constraints to model predictions, we conclude that CIRS is highly unlikely to see NH3 or CH3OH emissions. However, CH3CN and H2CO are closer to CIRS detectability, and we suggest ways in which the sensitivity threshold may be lowered towards this goal.
The flybys of Jupiter by the Voyager spacecraft in 1979, and over two decades later by Cassini in 2000, have provided us with unique datasets from two different epochs, allowing the investigation of seasonal change in the atmosphere. In this paper we
model zonal averages of thermal infrared spectra from the two instruments, Voyager 1 IRIS and Cassini CIRS, to retrieve the vertical and meridional profiles of temperature, and the abundances of the two minor hydrocarbons, acetylene (C2H2) and ethane (C2H6). The spatial variation of these gases is controlled by both chemistry and dynamics, and therefore their observed distribution gives us an insight into both processes. We find that the two gases paint quite different pictures of seasonal change. Whilst the 2-D cross-section of C2H6 abundance is slightly increased and more symmetric in 2000 (northern summer solstice) compared to 1979 (northern fall equinox), the major trend of equator to pole increase remains. For C2H2 on the other hand, the Voyager epoch exhibits almost no latitudinal variation, whilst the Cassini era shows a marked decrease polewards in both hemispheres. At the present time, these experimental findings are in advance of interpretation, as there are no published models of 2-D Jovian seasonal chemical variation available for comparison.
In this paper we select large spectral averages of data from the Cassini Composite Infrared Spectrometer (CIRS) obtained in limb-viewing mode at low latitudes (30S--30N), greatly increasing the path length and hence signal-to-noise ratio for opticall
y thin trace species such as propane. By modeling and subtracting the emissions of other gas species, we demonstrate that at least six infrared bands of propane are detected by CIRS, including two not previously identified in Titan spectra. Using a new line list for the range 1300-1400cm -1, along with an existing GEISA list, we retrieve propane abundances from two bands at 748 and 1376 cm-1. At 748 cm-1 we retrieve 4.2 +/- 0.5 x 10(-7) (1-sigma error) at 2 mbar, in good agreement with previous studies, although lack of hotbands in the present spectral atlas remains a problem. We also determine 5.7 +/- 0.8 x 10(-7) at 2 mbar from the 1376 cm-1 band - a value that is probably affected by systematic errors including continuum gradients due to haze and also an imperfect model of the n6 band of ethane. This study clearly shows for the first time the ubiquity of propanes emission bands across the thermal infrared spectrum of Titan, and points to an urgent need for further laboratory spectroscopy work, both to provide the line positions and intensities needed to model these bands, and also to further characterize haze spectral opacity. The present lack of accurate modeling capability for propane is an impediment not only for the measurement of propane itself, but also for the search for the emissions of new molecules in many spectral regions.
