Procena kvaliteta vode i sedimenta rečnog sliva AP Vojvodine i rizika po zdravlje u odnosu na prisustvo regulisanih i novootkrivenih mikropolutanata

The aim of this study was to determine the presence of 940 micro-contaminates including persistent organic compounds (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides), pesticides in current use, pharmaceutically active compounds, personal care products, sterols (human and terrestrial), n-alkanes (C9-C33) in surface water (rivers, canals, and lakes) and river sediments of the northern Serbian province, Vojvdina. The micro-contaminants were analyzed in the Danube, Tisza, Begej, and Krivaja rivers, the hydro system Danube–Tisza–Danube (DTD) as well as in two lakes Provala (near Bođani) and Tikvara (Bačka Palanka). The water samples were extracted by liquid-liquid extraction without any additional cleanup step. Sediment samples were extracted by using the pressurized liquid extraction technique and the extracts were purified by solid-phase extraction. The quantification of micro-contaminants was carried out by using gas chromatography coupled with single and triple mass spectrometry. The methods used for the analysis were validated to confirm their fitness for the purpose of determination of selected organic contaminants in surface water and sediment samples. The total number of qualified organic compounds in sediment and surface water samples was in the range of 85 to 117 and from 20 to 83, respectively. The total sum of quantified micropollutants in the sediment samples was in the range of 959 to 84 445 μg/kg and in the range of 1.35 to 55.1 μg/l in surface water samples. The obtained results were compared with the previously published data dealing with the determination of micropollutants in surface water and sediment worldwide. The ecological risk was evaluated through a comparison of quantified concentrations with the targeted values set by relevant regulations including the EU Water Framework Directive and subsequent Directive 2013/39/EU. Among the quantized compounds, the levels of polycyclic aromatic hydrocarbons, PAHs, (fluoranthene and benzo(a)pyrene) exceeded EU Environmental Quality Standards targeted values. The risk for the aquatic environment related to the presence of quantified micropollutants was evaluated by using relevant protocols widely used in similar studies. The human health risk assessment of quantified compounds in surface water was evaluated by using the protocol published by the US Environmental Protection Agency (USEPA). Carcinogenic and non-carcinogenic risks caused by dermal contact and non-intentional ingestion of water contaminated with micro-pollutants were evaluated. The results showed the absence of significant health risk for the human population. The chemometric techniques (principal component analysis and cluster analysis) were used in order to reveal the possible pollution sources of quantified compounds. The chemometric approach was successfully applied. It helped in the identification of locations where the simultaneous presence of different chemical groups was observed in extreme values. Additionally, the source identification of some classes of analyzed compounds (PAHs, sterols, n-alkanes) was evaluated by using their specific compound ratios which are unique for particular emission sources (e.g. pyrogenic or petrogenic source of PAHs). According to the obtained results, the following locations are separated from others as the most polluted: the Great Bačka Canal in Vrbas and Srbobran, and the sampling locations on the rivers Krivaja and Begej. A further monitoring program should be carried out on the mentioned sites to investigate the temporal trends for the presence of micro-contaminants. The obtained results were used for the identification of the Danube Basin-specific micropollutants in the investigated region. The selection of compounds to be included on the list is based on the frequency of occurrence and extent of exceedance of relevant regulated values.