The chemical and morphological transformations of condensed phase species of a thorium-based modifier were studied over the temperature range 200–2500 °C, without and with the presence of aluminium and silicon as matrix components, and in some instances, arsenic as an analyte element. A similar study was also conducted with palladium as the modifier, for comparison. Results were derived using scanning electron microscopy (SEM), energy dispersive (ED) X-ray spectrometry, Raman microanalysis and attenuated total reflectance (ATR) Fourier transform-infrared (FT-IR) spectrometry. Comparable results were found using pyrolytic and non-pyrolytic graphite platforms, with processes occurring at slightly higher temperatures on the pyrolytic graphite platform. With thorium as the modifier, metal oxides were the predominant species on the platform surface at relatively low temperatures (<1500 °C), whereas metal phases became prevalent at high temperatures, when thorium and aluminium tended to behave independently from one other. Some spatial variations in the composition of the salt residues on different regions of the platform were observed (from the region closest to the slot in the tube, to the region furthest from the slot). Nonetheless, thorium metal remained on the graphite platform to higher temperatures than did aluminium metal. In the presence of arsenic, the existence of mixtures of thorium and arsenic oxides, just before the appearance temperature of gas phase arsenic atoms, was confirmed by SEM studies, ED X-ray spectra and Raman microanalysis. This suggests that any modifying effect of thorium on arsenic occurs while the modifier is in the oxide phase rather than in the metal phase. The presence of silicon added as silica, did not influence significantly the thermochemical behaviour of mixtures of thorium and aluminium. However, coexistence of silicon and arsenic oxides at the appearance temperature of the atomic absorption signal of arsenic was obtained, confirming that silicon can act as an internal modifier for arsenic. In the presence of palladium, aluminium exhibited greater interaction with the modifier; consequently, aluminium metal was retained on the platform surface to higher temperatures than thorium, which could explain how interference effects of aluminium on e.g. arsenic are avoided or reduced. Similarly, there was evidence for interaction of palladium and arsenic in the reduced state. However, when aluminium and silicon were present, the transformation of the palladium oxide to the metallic state was affected, which could diminish the modifying benefits of palladium for arsenic in the presence of aluminium.