Industrial soils near Zn-Pb mines and metallurgical plants in the vicinity of Olkusz (southern Poland) are exposed to high environmental stress related to heavy metal pollution (Zn, Pb, Cd, Mn, Fe, Tl and As) from waste disposal sites and primary ores. X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectrometry analyses (EDS) and Atomic Absorption Spectroscopy (AAS) were used to analyse rhizosphere soil samples from the area. The mineral composition of the rhizosphere soils was determined. Carbonates of lead, cadmium and zinc, arsenic-lead sulphosalts and other minerals occurring on the root epiderm are described. Mineral aggregates of secondary origin include polymineralic spherules containing high concentrations of Zn (up to 2.3%), Pb (up to 0.7%), Fe (up to 23%), Cd (up to 427 mg kg −1 ) and Tl (up to 139 mg kg −1 ). Processes on the rhizoplane, and in the zone where plant-root exudation solutions are active, promote the crystallization of metalliferous minerals. ESEM is recommended as an efficient method for examining alteration occurring in the rhizosphere environment.

The soils adjacent to an area of historical mining, ore processing and smelting activities reflects the historical background and a mixing of recent contamination sources. The main anthropogenic sources of metals can be connected with historical and recent mine wastes, direct atmospheric deposition from mining and smelting processes and dust particles originating from open tailings ponds. Contaminated agriculture and forest soil samples with mining and smelting related pollutants were collected at different distances from the source of emission in the Pb-Zn-Ag mining area near Olkusz, Upper Silesia to (a) compare the chemical speciation of metals in agriculture and forest soils situated at the same distance from the point source of pollution (paired sampling design), (b) to evaluate the relationship between the distance from the polluter and the retention of the metals in the soil, (c) to describe mineralogy transformation of anthropogenic soil particles in the soils, and (d) to assess the effect of deposited fly ash vs. dumped mining/smelting waste on the mobility and bioavailability of metals in the soil. Forest soils are much more affected with smelting processes than agriculture soils. However, agriculture soils suffer from the downward metal migration more than the forest soils. The maximum concentrations of Pb, Zn, and Cd were detected in a forest soil profile near the smelter and reached about 25 g kg(- 1), 20 g kg(- 1) and 200 mg kg(- 1) for Pb, Zn and Cd, respectively. The metal pollutants from smelting processes are less stable under slightly alkaline soil pH then acidic due to the metal carbonates precipitation. Metal mobility ranges in the studied forest soils are as follows: Pb > Zn ≈ Cd for relatively circum-neutral soil pH (near the smelter), Cd > Zn > Pb for acidic soils (further from the smelter). Under relatively comparable pH conditions, the main soil properties influencing metal migration are total organic carbon and cation exchange capacity. The mobilization of Pb, Zn and Cd in soils depends on the persistence of the metal-containing particles in the atmosphere; the longer the time, the more abundant the stable forms. The dumped mining/smelting waste is less risk of easily mobilizable metal forms, however, downward metal migration especially due to the periodical leaching of the waste was observed.

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