Assessment of metal mobility, acid rock drainage production, and toxic effects from weathering of mineralised materials (ie mine-waste piles and outcropping alteration/ore zones) is key in evaluating and mitigating metal mining sites. Many metal- and acid-generating materials at these sites are sulfur minerals (sulfides to sulfates) with differing reactivities, weathering characteristics and metal contents. Our working hypothesis predicts that data on the types and quantities of sulfur minerals, coupled with comparison of their sulfur isotopic compositions to that of aqueous sulfate in the surrounding environment, can be used to evaluate primary pathways of weathering reactions at mining sites. We developed a sequential extraction scheme to separate the phases of sulfur in mineralised materials. Operationally defined phases, including monosulfides, disulfides, elemental sulfur, water-soluble sulfo-salts, acid-soluble sulfates, and resistant sulfate phases such as barite, are quantified gravimetrically and/or instrumentally. Several sets of experiments were designed to test the effectiveness of this extraction scheme. First, a variety of ore sulfides diluted in an inert matrix was analysed with the scheme. Results showed that molybdenite and arsenic-bearing sulfides do not behave as predicted from just their sulfur oxidation states, indicating that samples containing these minerals need special treatment for complete phase recovery. Second, a natural mine-waste composite standard was analysed by the scheme. The sum of the phases was equal to the total sulfur concentration analysed independently. Each phase had a similar, but distinct sulfur isotopic composition. The results were verified with a laboratory prepared proxy' having the same mineralogical composition as the standard, but with each phase having a very different sulfur isotopic composition. The sulfur isotopic compositions of the recovered phases from the proxy' showed that the scheme effectively separated the sulfur with only minor cross contamination of phases. The speciation and isotopic analyses were applied to both mine-waste piles and naturally occurring alteration zones at nine mine sites. A case study from one site comparing the sulfur isotopic composition of minerals in an alteration zone and dissolved sulfate in proximal streams is presented. This case study shows the application of our data to differentiating sources of sulfate in the surrounding environment.