The Imperial Smelting Furnace (ISF) for producing lead and zinc simultaneously has operated on four continents and in eleven countries from the 1950's. One of the process changes that the ISF introduced was the production of a finely granulated slag waste. Although this slag contained significant amounts of residual lead (Pb) and zinc (Zn), because of its glassy nature it was considered environmentally benign. From the Cockle Creek smelter near Boolaroo at the northern end of Lake Macquarie, NSW, Australia, it is estimated that around 2.1 million tonnes of the fine slag was distributed into the community and most remains where it was originally utilised. Residual tonnages of slag of this magnitude are common worldwide wherever the ISF operated. Studies of base metal smelting slags have concluded that mineralogical and morphological characteristics of the slag play a critical role in moderating environmental release of toxic elements. Scanning electron microscopy (SEM) and microanalysis of the ISF slags has shown that the Pb and associated elements are present as discrete nodules (∼6-22 μm) in the slag and that they are not associated with Zn which is contained in the glass slag phase. Using an automated SEM and analysis technique (QEMSCAN®) to "map" the mineralogical structure of the particles, it was possible to quantitatively determine the degree of access infiltrating fluids might have to the reaction surface of the Pb phases. The level of access decreases with increasing particle size, but in even the largest sized particles (-3350 + 2000 μm) nearly 80% of the Pb-containing phases were totally or partially accessible. These results provide evidence that the toxic elements in the slags are not contained by the glassy phase and will be vulnerable to leaching over time depending on their individual phase reactivity.