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Exploration of Mercury will continue in the near future with ESA/JAXA’s BepiColombo mission, which will increase the number and the type of datasets, and it will take advantage of the results from NASA’s MESSENGER (MErcury Surface, Space ENviroment, GEochemistry and Ranging) mission. One of the main discoveries from MESSENGER was the finding of a relatively high abundance of volatiles, and in particular of sulphur, on the surface. This discovery correlates well with the morphological evidence of pyroclastic activity and with features attributable to degassing processes like the hollows. BepiColombo will return compositional results from different spectral ranges and instruments, and, in particular, among them the first results from the orbit of emissivity in the thermal infrared. Here, we investigate the results from the emissivity spectra of different samples between a binary mixture of a volcanic regolith-like for Mercury and oldhamite (CaS). The acquisitions are taken at different temperatures in order to highlight potential shifts due to both mineral variation and temperature dependence on these materials that potentially could be present in hollows. Different absorption features are present for the two endmembers, making it possible to distinguish the oldhamite with respect to the regolith bulk analogue. We show how, in the mixtures, the Christiansen feature is strongly driven by the oldhamite, whereas the Reststrahlen minima are mainly dominated by mafic composition. The spectral contrast is strongly reduced in the mixtures with respect to the endmembers. The variations of spectral features are strong enough to be measured via MERTIS, and the spectral variations are stronger in relation to the mineralogy with respect to temperature dependence.