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|The mode of occurrence of metals in mine wastes is investigated using sequential extractions. Metals are extracted from some or all of seven operationally-defined phases: water-soluble, ion-exchangeable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, sulfide, and silicate. The quantity of metals extracted from each phase varies with particle size. The presence of jarosite (potassium end-member formula, KFe3[SO4]2[OH]6) influences the selection of the procedure for extracting the crystalline Fe-oxide phase. Anglesite (PbSO4) and cerussite (PbCO3) are extracted as several phases. Extraction results can be explained only in part by X-ray diffraction (XRD) mineralogy because of lack of specificity of the extraction procedures, relatively high XRD detection limits, and the presence of 40% XRD-amorphous matter in each waste. The increasing chemical strength of the sequentially applied methods provides a basis for judging metal availability, water-soluble metals being most available and silicate-bound metals being least available.|