Sorption of benzo[a]pyrene by Chernozem and carbonaceous sorbents: comparison of kinetics and interaction mechanisms.

Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon, highly persistent and toxic and a widespread environmental pollutant. Although various technologies have been developed to remove BaP from the environment, its sorption through solid matrixes has received increasing attention due to cost-effectiveness. The present research compares the adsorption capacity of Haplic Chernozem, granular activated carbon and biochar in relation to BaP from water solution. Laboratory experiments with different initial BaP concentrations in the liquid phase and different ratios of the solid and liquid phases show that Freundlich model describes well the adsorption isotherms of BaP by the soil and both sorbents. Moreover, the BaP isotherm sorption by the Haplic Chernozem is better illustrated by the Freundlich model than the Langmuir equation. The results reveal that the sorption capacity of the carbonaceous adsorbents at a ratio 1:20 (solid to liquid phases) is orders of magnitude higher (13 368 ng mL-1 of activated carbon and 3 578 ng mL-1 of biochar) compared to the soil (57.8 ng mL-1). At the ratio of 0.5:20, the adsorption capacity of the carbonaceous sorbents was 17-45 times higher than that of the soil. This is due to the higher pore volume and specific surface area of the carbonaceous sorbents than soil particles, assessed through scanning electron microscopy. The sorption kinetic of BaP by Chernozem was compared with the adsorption kinetics by the carbonaceous sorbents. Results indicate that the adsorption dynamic involves two steps. The first one is associated with a fast BaP adsorption on the large available surface and inside macro- and meso-pores of the sorbent particles of the granular activated carbon and biochar. Then, the adsorption is followed by a slower process of BaP penetration into the microporous space and/or redistribution into a hydrophobic fraction. The effectiveness of the sorption process depends on both the sorbent properties and the solvent competition. Overall, the granular activated carbon and biochar are highly effective adsorbents for BaP, whereas the Haplic Chernozem has a rather limited capacity to remove BaP from contaminated solutions.

Time effect on the stabilization of technogenic copper compounds in solid phases of Haplic Chernozem.

We studied the regularities of Cu stabilization in Haplic Chernozem contaminated with easily soluble (acetates, nitrates, sulfates, chlorides) and poorly soluble (acetates, nitrates, sulfates, chlorides) metal compounds in a five-year model experiment were studied. A low contents of Cu loosely bound compounds (LBC) (no >5% of total content) unchanging over time were revealed in the uncontaminated soil, which is indicative of the stability of soil processes. The Cu LBC content decreased over time in the soils contaminated with easily soluble compounds and increased in the soils contaminated with poorly soluble compounds. In both cases, the contents of Cu LBCs after 5 years of incubation remained higher than in the original uncontaminated soil. The effect of the attendant anions on the Cu LBC content was more apparent under the Cu application of 2000 mg kg-1 than at 300 mg kg-1. An inverse process characterized by an increase in the concentration of Cu LBCs over time was observed in the soil contaminated with Cu orthophosphate and oxide. Soil contaminated with different Cu compounds results in soil acidification. According to the effect on the decrease in soil pH, the attendant anions form the following series: SO42- ≈ Cl- > NO3- > Ac- > PO42- > O2-, which correlates with the Cu LBC content. Thus, the stabilization of Cu compounds in the soil is affected by the attendant anions and the interaction time of the metal with the soil solid phases.