Long-term dynamics of heavy metals in the upper horizons of soils in the region of a copper smelter impacts during the period of reduced emission

Abstract
The 23-year-long dynamics of actual acidity (pHwater) and acid-soluble heavy metals (Cu, Pb, Cd, Zn) in the forest litter and humus horizon of soils in spruce-fir forests were studied in the area subjected to the long-term (since 1940) pollution with atmospheric emissions from the Middle Ural Copper Smelter (Revda, Sverdlovsk oblast). For this purpose, 25 permanent sample plots were established on lower slopes at different distances from the enterprise (30, 7, 4, 2, and 1 km; 5 plots at each distance) in 1989. The emissions from the smelter have decreased since the early 1990s. In 2012, the emissions of sulfur dioxide and dust decreased by 100 and 40 times, respectively, as compared with the emissions in 1980. Samples of litter and humus horizons were collected on permanent plots in 1989, 1999, and 2012. The results indicate that the pH of the litter and humus horizons restored to the background level 10 and 23 years after the beginning of the reduction in emissions, respectively. However, these characteristics in the impact zone still somewhat differ from those in the background area. In 2012, the content of Cu in the litter decreased compared to 1989 on all the plots; the content of Cu in the humus horizon decreased only in the close vicinity of the smelter. The contents of other metals in the litter and humus horizons remain constant or increased (probably because of the pH-dependent decrease in migration capacity). The absence of pronounced removal of metals from soils results in the retention of high contamination risk and the conservation of the suppressed state of biota within the impact zone.