Smelting of base metal sulfide rich ore in Rouyn-Noranda, Québec, has led to the formation of black rock coatings on exposed rocks to a maximum distance of 6 km from the smelter centre. This study has shown that these coatings are excellent mineralogical and chemical fingerprints of smelter emissions, ore types, and elemental partitioning into mineral phases. The black coatings are composed of a silica-rich matrix that formed due to the intense chemical weathering of exposed silicate rocks interacting with acidic meteoric waters. They contain metal sulfate rich layers along the atmosphere-coating interface (ACI) and rock-coating interface (RCI) formed by the in situ dissolution and precipitation of metal(loid)-bearing phases. Entombed within the silica matrix are spherical particulates and particles composed of Cu- and Zn-bearing Fe oxides (e.g., spinels), Fe oxides (e.g., hematite), Pb silicates (e.g., alamosite), sulfates (anglesite (PbSO4) and minerals of the jarosite group), amphiboles, pyroxenes, micas, Na feldspar, and clinochlore. Concentrations of elements are low in proximity to the smelter but drastically increase ∼2 km from the stack, most likely the result of a shadow effect of the smelter. This shadow effect is more pronounced if an element is highly compatible with minerals of the jarosite and spinel groups; it is called the smelter-compatibility effect. Elements displaying a high smelter-compatibility effect are Ag, Cu, Se, and As, whereas elements such as Hg, which is incompatible with the jarosite and spinel groups, show a low smelter-compatibility effect. High δ34S (5.5‰) values in proximity to the smelter and their decrease with distance is the result of mixing processes between primary and secondary sulfates in the atmosphere. The relative enrichments of metal(loid)s in coatings at Rouyn-Noranda and Sudbury, Ontario, when normalised to the MUd standard from Queensland, Australia, (MUQ) reflect the composition of the smelter emissions, ore, and lithologies. Black rock coatings of the Rouyn-Noranda and Sudbury study areas are enriched, for example, in Pb and Fe, respectively, reflecting higher abundances of galena and Fe-bearing minerals in the respective ore, emissions, and rocks in the region.