Emissions from coal fired power stations are known to be a significant anthropogenic source of fine atmospheric particles, both through direct primary emissions and secondary formation of sulfate and nitrate from emissions of gaseous precursors. However, there is relatively little information available in the literature regarding the contribution emissions make to the ambient aerosol, particularly in the ultrafine size range. In this study, the contribution of emissions to particles smaller than 0.3 μm in the ambient aerosol was examined at a sampling site 7 km from two large Australian coal fired power stations equipped with fabric filters. A novel approach was employed using conditional sampling based on sulfur dioxide (SO₂) as an indicator species, and a relatively new sampler, the TSI Nanometer Aerosol Sampler. Samples were collected on transmission electron microscope (TEM) grids and examined using a combination of TEM imaging and energy dispersive X-ray (EDX) analysis for qualitative chemical analysis. The ultrafine aerosol in low SO₂ conditions was dominated by diesel soot from vehicle emissions, while significant quantities of particles, which were unstable under the electron beam, were observed in the high SO₂ samples. The behaviour of these particles was consistent with literature accounts of sulfate and nitrate species, believed to have been derived from precursor emissions from the power stations. A significant carbon peak was noted in the residues from the evaporated particles, suggesting that some secondary organic aerosol formation may also have been catalysed by these acid seed particles. No primary particulate material was observed in the minus 0.3 μm fraction. The results of this study indicate the contribution of species more commonly associated with gas to particle conversion may be more significant than expected, even close to source.