Despite international efforts to limit worker exposure to coal dust, it continues to impact the health of thousands of miners across Europe. Airborne coal dust has been studied to improve risk models and its control to protect workers. Particle size distribution analyses shows that using spraying systems to suppress airborne dusts can reduce particulate matter concentrations and that coals with higher ash yields produce finer dust. There are marked chemical differences between parent coals and relatively coarse deposited dusts (up to 500 µm, DD500). Enrichments in Ca, K, Ba, Se, Pb, Cr, Mo, Ni and especially As, Sn, Cu, Zn and Sb in the finest respirable dust fractions could originate from: (i) mechanical machinery wear; (ii) variations in coal mineralogy; (iii) coal fly ash used in shotcrete, and carbonates used to reduce the risk of explosions. Unusual enrichments in Ca in mine dusts are attributed to the use of such concrete, and elevated K to raised levels of phyllosilicate mineral matter. Sulphur concentrations are higher in the parent coal than in the DD500, probably due to relatively lower levels of organic matter. Mass concentrations of all elements observed in this study remained below occupational exposure limits.