The study used 276 urban soils and 447 rural soils collected from in and around the UK town of Northampton and focussed on the fractionation of Pb. The Pb fractionation obtained from total element data was compared to the fractionation of Pb in a subset of 10 urban soils obtained using a sequential extraction method. The fractionation of the Pb from the total element data and from the sequential extractions was estimated using a self-modelling mixture resolution statistical model. The bioaccessibility of Pb in a subset of 50 of the urban soils, as measured using the unified BARGE method, was shown to be quantitatively linked with Pb fractionation from both the total element and the sequential extraction data. Three intrinsic soil components from the regional total element data model and one physico-chemical component from the sequential extraction data model were identified as the sources of bioaccessible Pb. The source of bioaccessible Pb in both rural and urban soils was tentatively identified as a fine-grained pyromorphite mineral.