Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale
Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO 2 ) at or near the nominal solid-phase laboratory wavelength of 4.2675 ??m (2343.3 cm -1 ), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO 2 absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO 2 , CO 2 clathrates, ternary mixtures of CO 2 with other volatiles, implanted and adsorbed CO 2 in non-volatile materials, and ab initio theoretical calculations of CO 2 * nH 2 O. At the wavelength resolution of VIMS, the CO 2 on Phoebe is indistinguishable from pure CO 2 ice (each molecule's nearby neighbors are also CO 2 ) or type II clathrate of CO 2 in H 2 O. In contrast, the CO 2 band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ???4.255 ??m (???2350.2 cm -1 )) and broadened. These wavelengths are characteristic of complexes of CO 2 with different near-neighbor molecules that are encountered in other volatile mixtures such as with H 2 O and CH 3 OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe's CO 2 is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO 2 on the other three satellites results at least in part from particle or UV irradiation of native H 2 O plus a source of C, implantation or accretion from external sources, or redistribution of native CO 2 from the interior. The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 ??m, apparently as a consequence of telluric CO 2 gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector response profiles with a deep atmospheric CO 2 absorption profile, producing distorted detector profile shapes and shifted central positions. In a laboratory blackbody spectrum used for radiance calibration, close examination of the CO 2 absorption profile shows a similar deviation from that expected from a model. These modeled effects appear to be sufficient to explain the distortion in the existing wavelength calibration now in use. A modification to the wavelength calibration for 13 adjacent bands is provided. The affected channels span about 0.2 ??m centered on 4.28 ??m. The maximum wavelength change is about 10 nm toward longer wavelength. This adjustment has implications for interpretation of some of the spectral features observed in the affected wavelength interval, such as from CO 2 , as discussed in this paper.