Airborne particulate matter has been collected from within, and proximal to, an opencast coal mine in south Wales. This work forms the first part of a three year project to collect and characterise, then determine the possible toxicology of airborne particles in the south Wales region. High-resolution Field Emission SEM has shown that the coal mine dusts consist largely of an assemblage of mineral grains and vehicle exhaust particles. SEM-EDX has shown that the mineralogical make-up of the PM10 is complex, heterogeneous, and constantly changing. These findings are supported by analytical TEM-EPXMA. However, patterns can be determined relating the mineralogical composition of the airborne particles to collection locations and mining activities within the opencast. At our study opencast, Park Slip West, quartz, which has known health effects, never exceeded 30% of the total collection mass, and average levels were much less. Vehicle exhaust emissions was the largest source in terms of particle numbers. The mass of airborne particulate matter within the pit averaged approximately twice that of outside the pit: importantly however, this higher mass was due to relatively large, and non-respirable, mineral grains. This study demonstrates that the physicochemical and mineralogical characterisation of airborne particles from mining and quarrying is essential to quantify the respirable fraction, and to identify potentially hazardous components within the PM10.