Aerosol dust samples and quartz raw materials from different working stations in foundry plants were characterized in order to assess the health risk in this working environment. Samples were analysed by scanning and transmission electron microscopy coupled with image analysis and microanalysis, and by cathodoluminescence spectroscopy. In addition, the concentration and the solubility degree of Fe and other metals of potential health effect (Mn, Zn and Pb) in the bulk samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). Overall, the results indicate substantial changes in quartz crystal structure and texture when passing from the raw material to the airborne dust, which include lattice defects, non-bridging oxygen hole centres and contamination of quartz grains by metal and/or graphite particles. All these aspects point towards the relevance of surface properties on reactivity. Exposure doses have been estimated based on surface area, and compared with threshold levels resulting from toxicology. The possible synergistic effects of concomitant exposure to inhalable magnetite, quartz and/or graphite particles in the same working environment have been properly remarked.