The aims of this work are to provide a detailed physicochemical assessment of atmospheric particles collected in the vicinity of three iron and steelmaking plants and to indicate the importance of chemical characterisation of the particles, in addition to the assessment of the particle size and concentrations. In this study, atmospheric sampling sites were selected downstream of three iron and steel processing operations in Australia and one background site in an urban area with little industrial activity. The collected particles were analysed for a range of particle size mass concentrations and detailed chemical analysis of the trace metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn in the corresponding particle size ranges was carried out. The PM2.5 fractions in the PM10 particles at all sampling sites ranged from 35 to 62% indicating fine particles made a significant contribution to this size fraction at these sampling sites. Similarly, PM1 to the total PM10 at all sites varied from 20 to 46% and contributed significantly to the PM10 mass loading. When compared to the background sampling site, all detected metals in the particles collected near the iron and steelmaking operations had 3.4-14 times higher concentrations of PM10, PM2.5 and PM1. Iron (Fe) was found to be the dominant metal in the particles collected in vicinity of the iron and steel processing industries contributing up to 12% of the total particle mass loading. This study suggests that the metal composition of PM10, PM2.5 and PM1 varies significantly between sites and the associated metal exposure value is considerably higher in the vicinity of iron and steel processing industries than in the urban area for the same particle concentration level.