Accumulation of heavy metal(loid)s and polycyclic aromatic hydrocarbons in the sediment of the Prahovo Port (Danube) and associated risks

The current study investigated the concentrations, possible sources, toxicity, and ecological risk of eight heavy metal(loid)s (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) and sixteen priority polycyclic aromatic hydrocarbons (PAHs) in surface sediments in the port of Prahovo (Danube, Serbia). Among the examined HMs, the most abundant was Cu (38.3 mg/kg), followed by Zn. The Σ16PAHs concentrations ranged from 25 to 112.5 µg/kg, with 4-ring PAHs (17.3 µg/kg) being the most dominant in the study area. The mean and maximum values of HMs and PAHs obtained in this study were below the national regulatory limits and within environmental criteria. Particularly significant correlations between As, Cd, Cr, Ni, Pb, Zn, 5-, 6-ring PAHs, as well as between Pb and Hg, indicated their similar anthropogenic sources, pathways, and adsorption mechanisms. These findings were confirmed by cluster analysis and principal component analysis. Diagnostic ratios demonstrated that contamination in inner port stations was characterized by pyrogenic sources, while PAHs of petrogenic origin prevailed in samples near the port entrance. The mean ERM quotient (mERMq), toxic risk index (TRI), and toxic equivalent quotient (TEQ) were also calculated to assess the toxicity of the investigated HMs and PAHs in sediments. Positive matrix factorization suggested four potential sources as the main components of sediment contamination, whereas the risk assessment indicated a low or relatively insignificant risk of adverse biological effects from the combined toxicity of HMs and PAHs for the entire study area.