A range of carbon nanoparticles, agglomerates and mineral phases have been identified in burning coal waste pile materials from the Douro Coalfield of Portugal, as a basis for identifying their potential environmental and human health impacts. The fragile nature and fine particle size of these materials required novel characterization methods, including energy-dispersive X-ray spectrometry (EDS), field-emission scanning electron microscope (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM) techniques. The chemical composition and possible correlations with morphology of the nanominerals and associated ultra-fine particles have been evaluated in the context of human health exposure, as well as in relation to management of such components in coal-fire environments.