The Lead Pathway Air Study (2007-2012) on the human exposure to lead was undertaken at Mount Isa, Queensland, Australia. Mount Isa Mines is located west of the city and mined and processed lead-zinc and copper ores since the 1930s. The Australian health risk assessment framework was followed using bioavailability and bioaccessibility tests and other measurements. Human exposure to lead is from ingestion of ≤250 µm sized particles via the digestive system and inhalation of <10 µm sized particles into lungs; absorption via skin is insignificant. This paper considers the relationship of lead speciation data and bioaccessibility/bioavailability with characteristics of mine waste and environment samples for human health risk assessment. Sampling provided physico-chemical characteristics together with high resolution lead isotope measurements and other techniques (XRD, SEM and particle size analysis). Synchrotron-based X-ray absorption spectroscopy (XAS) using x-ray absorption near-edge spectroscopy (XANES) recorded lead LIII-edge spectra at BL 20B, Photon Factory,Tsukuba, Japan. Lead speciation/composition in the recorded spectra of over 300 samples were fitted using linear combination fitting (LCF) of sample spectra against up to 20 model compounds. Bioaccessibility (BAc) was measured using the Physiologically Based Extraction Test (PBET) to simulate the gastrointestinal tract of pH 1.3, 2.5 and 4.0 for fasting, partially fed and fed stomach conditions respectively, and pH 7.0 for the small intestine. Predicted bioaccessibility from XANES spectra LCF with model Pb compounds showed no significant difference from measured BAc (p >0.05). Lead BAc in all mine wastes was 32±21% (mean ± sd; n=82) compared with 24±12% (mean ± sd; n=99) in surrounding city garden soil; only a small proportion of lead was available for absorption. A significant correlation (r²=0.656, n=12) showed that BAc can be used to predict bioavailability, calculated from bioaccessibility of 10 representative data sets and based on the upper 95 per cent confidence interval level for slope (0.17) of the line fitted through zero for bioavailability where %ABA=%BAc x 0.17. XANES analysis showed that samples from both mining and processing areas contained lead sulfide (PbS), but absent from other sources. Thus the various forms of lead from different sources could be related to quantities potentially available for ingestion and/or inhalation exposure by the Mount Isa community.