Abstract Most current investigations of sites contaminated with heavy metals (e.g. Pb, Zn, Cu) emphasise the importance of determining the amounts of physical and chemical forms of metals rather than just the total amounts present. Chemical extraction techniques used for this purpose are inevitably operationally defined. A more direct approach to the identification of crystalline forms can be made by mineralogical techniques such as X-ray powder diffraction (XRPD), but quantitative determination of a particular form is not often attempted. Recent advances in methods of analysis and sample preparation for XRPD mean that it is now a relatively simple matter to obtain quantitative XRPD data. Here, it is applied to the quantitative determination of the forms of Pb in different size-fractions of stream sediment samples from Leadhills/Wanlockhead, SW Scotland, an historic Pb mining area. Comparison of the XRPD analyses with determinations of Pb by atomic absorption spectrophotometry demonstrates that a large proportion of the Pb present in the stream sediments is in the form of cerussite (PbCO 3). Furthermore, the cerussite tends to be concentrated in the silt fraction and is even a minor component of the clay-size fraction. However, quantitative analysis of fractions <6 μm indicates that cerussite alone cannot account for all the Pb in this size range. Indirectly, this result suggests that Pb adsorbed to clay minerals, organic matter and/or amorphous Fe and Mn oxides may be proportionally more important for the <6 μm materials. Sediment in this size range, however, typically accounts for no more than 1% by weight of the total stream bed sediment samples collected in the study area. In relation to its size distribution, the mobility of Pb within the wider environment is most likely to occur principally through physical transport of fine particles.