Environmental and human health risk assessments of nanoparticle effects from coal and bottom ash require thorough characterisation of nanoparticles and their aggregates. In this manuscript, we expand the study of human exposure to nanosized particles from coal combustion sources (typically <100 nm in size), characterising the complex micromineralogy of these airborne combustion-derived nanomaterials. Our study focuses on bottom ash generated in the Santa Catarina power station (Brazil) which uses coal enriched in ashes, many potential elements (e.g. Cr and Ni) and pyrite. Transmission electron microscope data reveal nanoscale C deposits juxtaposed with and overgrown by slightly larger aluminosilicate (Al-Si) glassy spheres, oxides, silicates, carbonated, phosphates and sulphates. Iron oxides (mainly hematite and magnetite) are the main bottom ash products of the oxidation of pyrite, sometimes via intermediate pyrrhotite formation. The presence of iron oxide nanocrystals mixed with silicate glass particles emphasises the complexity of coal and bottom ash micromineralogy. Given the potentially bioreactive nature of such transition metal-bearing materials, there is likely to be an increased health risk associated with their inhalation.