To assess the potential impact of metal and acid contamination from mine-waste piles, it is important to identify the mineralogic source of trace metals and their mode of occurrence. Microscopic analysis of mine-waste samples from both hard-rock and coalmine waste samples demonstrate a microstructural control, as well as mineralogic control, on the source and release of trace metals into local water systems. The samples discussed herein show multiple periods of sulfide mineralization with varying concentrations of trace metals. In the first case study, two proprietary hard-rock mine-waste samples exposed to a series of humidity cell tests (which simulate intense chemical weathering conditions) generated acid and released trace metals. Some trace elements of interest were: arsenic (45-120 ppm), copper (60-320 ppm), and zinc (30-2,500 ppm). Untested and humidity cell-exposed samples were studied by X-ray diffraction, scanning electron microscope with energy dispersive X-ray (SEM/EDX), and electron microprobe analysis. Studies of one sample set revealed arsenic-bearing pyrite in early iron- and magnesium-rich carbonate-filled microveins, and iron-, copper-, arsenic-, antimony-bearing sulfides in later crosscutting silica-filled microveins. Post humidity cell tests indicated that the carbonate minerals were removed by leaching in the humidity cells, exposing pyrite to oxidative conditions. However, sulfides in the silica-filled veins were more protected. Therefore, the trace metals contained in the sulfides within the silica-filled microveins may be released to the surface and (or) ground water system more slowly over a greater time period. In the second case study, trace metal-rich pyrite-bearing coals from the Warrior Basin, Alabama were analyzed. Arsenic-bearing pyrite was observed in a late-stage pyrite phase in microfaults and microveins that crosscut earlier arsenic.