The investigation presented here was conducted during a wider experiment on the technical feasibility and environmental impacts of tire combustion in a Brazilian coal-fired power station. Nanometric-sized crystalline phases in fly ash were characterised using energy-dispersive X-ray spectrometer (EDS) and high-resolution transmission electron microscopy (HR-TEM) images. The nanoparticles, which register abundance peaks at 10 nm and 100 nm, include iron-rich oxide (e.g. hematite), Fe-sulphate (e.g., yavapaiite: KFe(SO4)2), and Fe-aluminumsilicate glass. Individual metalliferous nanoparticles have a heterogeneous microstructure in which elements such as iron, aluminum and silicon are not uniformly distributed. HR-TEM offers a powerful analytical technique in the study of fly ash nanoparticles, providing a better understanding of the detailed chemistry of this potentially strongly bioreactive component of atmospheric particulate matter.