We report on the discovery of an infrared emission band in the Spitzer spectrum of the S-type AGB star NP Aurigae that is caused by TiO molecules in the circumstellar environment. We modelled the observed emission to derive the temperature of the TiO
molecules (approx 600 K), an upper limit on the column density (approx 10^17.25 cm^{-2}) and a lower limit on the spatial extent of the layer that contains these molecules. (approx 4.6 stellar radii). This is the first time that this TiO emission band is observed. A search for similar emission features in the sample of S-type stars yielded two additional candidates. However, owing to the additional dust emission, the identification is less stringent. By comparing the stellar characteristics of NP Aur to those of the other stars in our sample, we find that all stars with TiO emission show large-amplitude pulsations, s-process enrichment, and a low C/O ratio. These characteristics might be necessary requirements for a star to show TiO in emission, but they are not sufficient.
S-type AGB stars are thought to be in the transitional phase between M-type and C-type AGB stars. Because of their peculiar chemical composition, one may expect a strong influence of the stellar C/O ratio on the molecular chemistry and the mineralogy
of the circumstellar dust. In this paper, we present a large sample of 87 intrinsic galactic S-type AGB stars, observed at infrared wavelengths with the Spitzer Space Telescope, and supplemented with ground-based optical data. On the one hand, we derive the stellar parameters from the optical spectroscopy and photometry, using a grid of model atmospheres. On the other, we decompose the infrared spectra to quantify the flux-contributions from the different dust species. Finally, we compare the independently determined stellar parameters and dust properties. For the stars without significant dust emission, we detect a strict relation between the presence of SiS absorption in the Spitzer spectra and the C/O ratio of the stellar atmosphere. These absorption bands can thus be used as an additional diagnostic for the C/O ratio. For stars with significant dust emission, we define three groups, based on the relative contribution of certain dust species to the infrared flux. We find a strong link between group-membership and C/O ratio. We show that these groups can be explained by assuming that the dust-condensation can be cut short before silicates are produced, while the remaining free atoms and molecules can then form the observed magnesium sulfides or the carriers of the unidentified 13 and 20 micron features. Finally, we present the detection of emission features attributed to molecules and dust characteristic to C-type stars, such as molecular SiS, hydrocarbons and magnesium sulfide grains. We show that we often detect magnesium sulfides together with molecular SiS and we propose that it is formed by a reaction of SiS molecules with Mg.
