Oral bioaccessibility and solid phase distribution of potentially toxic elements (PTE) from extractive waste streams were investigated to assess the potential human health risk posed by abandoned mines. The solid phase distribution along with micro-X-ray fluorescence (micro-XRF) and scanning electron microscopy (SEM) analysis were also performed. The results showed that the total concentrations of PTE were higher in <250 μm size fractions of waste rock and soil samples in comparison to the <2 mm size fractions. Mean value of total concentrations of chromium(Cr), copper (Cu), and nickel (Ni) in waste rocks (size fractions <250 μm) were found to be 1299, 1570, and 4010 mg/kg respectively due to the parent material. However, only 11% of Ni in this sample was orally bioaccessible. Detailed analysis of the oral bioaccessible fraction (BAF, reported as the ratio of highest bioaccessible concentration compared with the total concentration from the 250 μm fraction) across all samples showed that Cr, Cu, and Ni varied from 1 to 6%, 14 to 47%, and 5 to 21%, respectively. The variation can be attributed to the difference in pH, organic matter content and mineralogical composition of the samples. Non-specific sequential extraction showed that the non-mobile forms of PTE were associated with the clay and Fe oxide components of the environmental matrices. The present study demonstrates how oral bioaccessibility, solid phase distribution and mineralogical analysis can provide insights into the distribution, fate and behaviour of PTE in waste streams from abandoned mine sites and inform human health risk posed by such sites.