Micro-pollutants in sediment samples in the middle Danube region, Serbia: occurrence and risk assessment

This is the first comprehensive study on the occurrence of 940 semi-volatile organic compounds including sterols, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pesticides, plasticizers, and other emerging compounds in 10 river and canal sediments collected in northern Serbia. For quantification of investigated compounds GC-MS-MS (selected reaction monitoring) and GC-MS (using both selected ion monitoring and total ion monitoring) methods were used. The number of detected compounds was in the range of 85–117, while the sum of the concentrations varied from 959 μg/kg dry-wt to 84,445 μg/kg dry-wt. Sterols were quantified with high frequency in nearly 100% of investigated samples suggesting that the studied rivers and canals have been contaminated by sewage. Regarding persistent organic compounds, p,p′-DDE, p,p′-DDD, and o,p′-DDT were the dominant members of organochlorine pesticides (OCPs). The concentration range of 11 quantified pesticides of 452 analyzed was from 0.564 to 61.6 μg/kg dry-wt, while the concentration range of 47 quantified PCBs of 90 analyzed was from 0.928 to 32.1 μg/kg dry-wt. OCPs (DDE, DDD, and γ-HCH) and several PAHs (fluoranthene, pyrene, phenanthrene, chrysene, benzo(a)anthracene, benzo(a)pyrene) exceeded the maximum values of the sediment quality guidelines. Contents of domestic compounds comprise a large proportion of the total contaminant concentration. Overall, the study reveals that river sediments in Vojvodina Province were moderately polluted mainly by domestic wastewater. The toxic equivalent quantity (TEQ) relative to benzo(a)pyrene and 2,3,7,8-tetrachlorodibenzodioxin for seven carcinogenic PAHs and six quantified dioxin-like PCBs ranged from 3.59 to 103 μg TEQ/kg and from 0.001 × 10⁻³ to 2.10 × 10⁻³ μg TEQ/kg, respectively, and were in the range or lower than the literature published data.