Neutral and slightly alkaline arable soils from the vicinity of the former and the biggest metallurgical plant in southeastern Europe were analyzed for the status of the water soluble pool of heavy metals in 1–20% w/w biochar (BC)-amended contaminated soils. Heavy metal solubility was monitored over a 6-month period. The metals (Fe, Mn, Cu, Zn, Cd, Pb and Ba) exhibited significant relationships between each other and exceeded the maximum permissible concentrations (MPC) in surface waters for domestic and drinking purposes. In most of the investigated sites and BC treatments, metal concentrations decreased with time due to the transfer to more resistant soil pools. Cation exchange capacity, exchangeable Ca and pH increased after BC application, while electrical conductivity decreased. BC amendment led to the prevalence of humic acids (HAs) over fulvic acids (FAs) and increased the fraction of refractory organic carbon. The share of metal–organic complexes increased for the metals Zn, Cd, Mn and Ba in the BC-amended soils, and the share of free Me²⁺ species decreased. This trend was especially pronounced in the soils with the lowest pH of 6.4–6.9. In addition to improving soil physicochemical and ecochemical properties, biochar application contributed to metal species in solutions that were less mobile and bioavailable.

The present study describes signature lipid biomarkers in reclaimed mine soils (RMSs), an unreclaimed spoil and a natural soil (Vertisol) for a major coal mine basin in Eastern Europe. Alkanes, fatty acids and fatty alcohols, as well as coal biomarkers were abundant in the mine soils and the unreclaimed spoil. The alkanes distribution in the RMSs was bimodal with maxima at C₁₈ and C₂₉/C₃₁ and points at two origins for the alkanes, terrigenous plants, including soil borne and from the coal source. Fatty acid carbon preference indices (CPI_even/odd = 10.4 and 8.1 for the mine soils under pine and grass vegetation) reflect the increasing role of terrestrial vegetation in the formation of organic matter. The higher concentrations of the long-chain alkanes, fatty acids and alcohols are speculated as the reason for the severe and extreme water repellency observed with the Vertisol and the unreclaimed spoil. The presence of terrigenous steroid and triterpenoid markers in the RMSs is an indication of the ongoing soil formation processes. The analysis of lipid extracts allowed for the assessment of sensitive molecular indicators of biogenic terrigenous and coal origin and the degree of soil recovery following >20 years of spoils reclamation.

The efforts of researchers to find suitable and cost-effective technologies for restoration of heavy metal polluted lands are continuous. In Bulgaria, this problem is acute especially around several big metallurgical plants for mining and processing of metals, such as Aurubis-Pirdop copper smelter, Asarel-Medet open mining plant, the former Kremikovtsi smelter, etc. Some of these point sources of contamination are already closed, others use new technologies that lead to minimized environmental risk. Efforts are focused on the ways to reduce environmental impact of heavy metals by decreasing their mobility in soils and access to ground waters, as well as their availability to plants.