Metallurgical pretreatment of As-bearing ores involves oxidation of sulphides (most often As-bearing pyrite, arsenopyrite or enargite) resulting in complex oxidized As-bearing products. We have evaluated roasting pretreatment of arsenic-bearing ores in a broad context and related this to the specific operations at the Giant mine, Yellowknife, NWT, Canada, which roasted arsenopyrite (FeAsS)-rich gold ore concentrates during 50 years of operations. A large portion of the As was collected and stored in underground vaults as As2O3 dust; however, some of the As was also released with tailings which contain concentrations between 1000 to 5000 ppm. Powder X-ray diffraction (XRD) and sequential extractions have been completed on samples of mill products and various ages of tailings at the Giant mine. These data along with petrographic and synchrotron μXRD and μX-ray absorption near-edge spectroscopy (μXANES) indicate that the largely oxidized roaster products (calcine) and electrostatic precipitator (ESP) dust host most of the As in the tailings with a lesser component of sulphide arsenic. The fine-grained nature of these oxidized products has led to hydraulic sorting within the tailings impounds and dispersal to downstream creek and lake sediments.