Oxidation zones of ore deposits offer valuable insights into the long-term fate of many metals and metalloids. In this work, we have studied a paleo-acid rock drainage (ARD) system – the oxidation zone of Mississippi-valley type Zn–Pb deposits near Olkusz in southern Poland. The ARD systems exhausted their acid-generating capacity and have come almost to the conclusion of the mineral and geochemical transformations. Primary pyrite, marcasite, galena and sphalerite have been decomposed but the acidity was neutralized by the abundant carbonate host rocks. Zinc is stored in smithsonite, hemimorphite, and Zn-rich sheet aluminosilicates. Some of these minerals formed simultaneously with the oxidation zone but some precipitated in the soils in situ, thus documenting the mobility of Zn, Al, and Si in the soils. Iron oxides are represented mostly by goethite, either well-crystalline or nanocrystalline, as determined by a combination of powder X-ray diffraction, micro-X-ray diffraction, and Mössbauer spectroscopy. Iron oxides bind a substantial amount of arsenic, to a lesser extent also zinc, lead, and cadmium, as shown by electron microprobe analyses and sequential extractions. The X-ray absorption spectroscopy data of the local environment of arsenic in goethite suggest the existence of bidentate mononuclear complex, in addition to the more common bidentate binuclear complex. These results suggest that arsenic is incorporated in the crystal structure of goethite, in addition to adsorbed to the surface of the particles or occluded in the voids and pores. Zinc is bound in goethite as a mixture of tetrahedrally and octahedrally coordinated cations. This study shows that the mature system binds the metals from the primary sulfides relatively strongly. Yet, some release of the metals was observed in this study, either in the laboratory (by sequential extractions) and in nature (e.g., neoformed Zn phyllosilicates). The physical conditions in the oxidation zone and on the surface are largely similar but the metals, to a certain extent, are still mobile in the soils. We may speculate that their mobility near the surface, in the mining waste, may be enhanced by a higher water/rock ratio than in the oxidation zone. This result implies that although the studied material is relatively benign, it still has a potential to cause local environmental problems.