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Black rock-coatings occur in proximity to smelters and roast yards of the Greater Sudbury area, Ontario, Canada and contain information about the past interactions between surface minerals, and gaseous and particulate atmospheric components, many of which were pollutants. Rock-coatings were collected from various locations within the Sudbury area and are characterized with scanning electron microscopy, transmission electron microscopy, X-ray diffraction, electron microprobe analysis, infrared spectroscopy and X-ray photoelectron spectroscopy. Acidic fumigations and rain, the result of vast quantities of SO2 released from smelting, increased the chemical weathering rate of exposed rocks in the Sudbury area. Non-stoichiometric dissolution of the silicate minerals under acidic conditions resulted in the accumulation of silicic acid and the subsequent formation of a silica-gel type coating. The silica gel transformed overtime into amorphous silica, opal (opal C and opal-CT) and cristobalite. Dissolution of the underlying rock and also of metal-bearing particles by sulfuric acid resulted in the in situ formation of metal-sulfate-rich layers on the interfaces between the atmosphere and the silica-rich coating (atmosphere-coating interface, ACI) and between the silica-rich coating and the underlying rock (rock-coating interface, RCI). These metal-sulfate-rich layers contain nanometer aggregates of Fe-Cu-sulfate-hydroxide, goldichite, mereiterite, guildite, butlerite and antlerite. The silica-rich matrix also contains a mix of detrital grains from adjacent rocks and soils (feldspar, quartz, hematite, chlorite, montmorillonite) and non-dissolved smelter-derived nano-to micro-size particulates (metal-silicates, metal-oxides, C-spheres). The apparent disequilibrium between the embedded particles and the Fe-Cu-sulfates suggests that trapped nanoparticles were encapsulated into pores which prevented their equilibration with acidic metal-sulfate-bearing fluids. An XPS depth profile indicates a gradual transition from lower to higher concentrations of metals from the coating surface towards the metal-sulfate-rich layer on the ACI, which suggests that the outer surface of the coatings is currently leached on an angstrom scale by surface waters. (C) 2012 Elsevier Ltd. All rights reserved.