In acid base accounting (ABA) estimates of acid mine wastes, the acid potential (AP) estimate can be improved by using the net carbonate value (NCV) reactive sulfide S method rather than total S assay methods but this does not give recovery of potentially acid producing ferrous and ferric sulfates present in many wastes. For more accurate estimation of AP, an effective, site-specific method to quantify acid sulfate salts, such as jarosite and melanterite, in waste rocks has been developed and tested on synthetic and real wastes. The SPOCAS (acid sulfate soils) methods have been modified to an effective, rapid method to speciate sulfate forms in different synthetic waste samples. A three-step sequential extraction procedure has been established. These steps are: (1) argon-purged water extraction (3 min) to extract soluble Fe(II) salts (particularly melanterite), epsomite and gypsum (<10 wt.%), (2) roasting at 550 degrees C (1 h) to remove sulfur from pyrite and other reactive sulfides, (3) HCl extraction (4 M, 30 min) for determination of jarosites. Products (solid and aqueous) have been characterized at each step including the jarosite decomposition process in Step 2 where temperature control is critical to avoid S loss. The sequential extraction procedure was used to quantitatively determine melanterite, epsomite, gypsum, pyrite and jarosite concentrations in a synthetic waste sample containing these mineral phases at 5 wt.% in quartz, and also tested using a tailings waste sample to quantitatively determine epsomite, gypsum and jarosite contents. The method is applicable to most waste samples including those with non-pyrite sulfides but for samples containing significant amounts of sulfur (>1 wt.% S) as copper sulfides, the second step of roasting needs to be excluded from the procedure with an increased time of 4 M HCl extraction to 16 h for jarosite determination.