A geochemical background characterization was conducted on numerous soil and sediment profiles in the Stawell region in NW Victoria, Australia. The aim of the research was to understand regional chemical baselines and the mineralogical phases associated with elements that may pose a potential environmental threat. The Stawell region and the mine site are associated with elevated As levels and the Stawell Gold Mine was concerned about potential environmental hazards. In addition to regional samples, surface soil samples were taken from the area immediately surrounding the Stawell Gold Mine. Samples were subject to a sequential leach extraction, total acid digestion and a bioavailable leach. Arsenic was thought to be a serious problem in the soils surrounding the mine, total metal concentrations ranged from 15.9 - 946 mg/kg; however the bioavailable As content was much lower, averaging 0.5% of Total As. All leaches revealed low quantities of As, as well as most others of environmental concern including Cd, Cr, Cu, Ni and Pb. Maximum bioavailable As, Pb and Cu were 5.6, 17.3 and 1.6 mg/kg, respectively. All other potentially toxic metals had less than 1 mg/kg bioavailable concentrations. Statistical analysis revealed that total soil Pb, Zn and Mn concentrations were highly correlated to bioavailable concentrations, while As was not. Total As was highest around the mine site, while bioavailable As was highest near the township. The sequential extraction revealed that some elements were primarily associated with specific mineral phases, particularly the organic phase for As and Fe-oxide phase for Pb. The regional geochemical backgrounds are not excessively high and the exposure assessment indicates there is little risk to human health with all analysed elements under the ANZECC guidelines.