Summary:
The environmental problems in the Black Sea resulting from anthropogenic activities are mainly pollution and eutrophication process, accompanied by natural variability and climatic changes. However, anthropogenic activities are with no doubt presently the powerful driver of change in its ecosystem. In the Black Sea coasts, uncontrolled industrial and domestic wastes are either deposited into or stored at a variety of land and water-based disposal sites. Environmental crisis of the Black Sea is well related to the unique characteristics of the marine environment.
The term “emerging pollutants” (EPs) or “emerging contaminants” (ECs) refers to compounds and their metabolites that are not included in regular monitoring studies, are not currently covered by existing water-quality regulations, and are thought to be potential threats to environmental ecosystems and human health and safety.
The Water Framework Directive (WFD) (2000/60/EC) sets a comprehensive management planning system to help protect and improve the ecological and chemical status of Black Sea, and in general all European water bodies. Recent advances and improvements in analytical techniques, and especially in high resolution mass spectrometry, have given the opportunity to scientific groups to detect and identify a huge number of chemical compounds, even in complex matrices. LC-HRMS allows the wide-scope screening of ECs and their (bio) TPs.
The aim of this thesis is the determination of emerging contaminants with a wide LC-ESI-Q-ToF target screening methodology of more than 2000 compounds. The sea water samples were purified with SPE method and used HLB cartridges, sediments were purified with ultrasonic extraction and biota samples with 2-days generic extraction before the analysis.Extracts were analyzed with reversed-phase liquid-chromatography coupled to quadrupole-time-of-flight mass spectrometry (RPLC-QTOF-MS) with positive and negative electrospray ionization and the data were acquired through data dependent and data independent acquisition mode (bbCID and Auto-MS scan modes).
The study area for contamination state was covered by three transects of Black Sea; the western side close to Ukraine/Romania (Danube Delta), the eastern Black Sea close to Georgia and the central side including (Open Sea) sampling points across the length of Black Sea and out of reach of any coastal city. Twenty one seawater samples (seven Open Sea, seven UA (Ukraine) and seven GE (Georgia)) were collected and analyzed. The results indicate the presence of Phthalates (including Dimethyl-phthalate and Benzyl butyl-phthalate), also eleven phenols were determined in seawater samples like 2,4-Dinitrophenol (DNP) which presented high frequency of detection among all analyzed samples. Moreover, PFCs were detected like PFOA, PFHxA and GENX but most were in low concentrations. Also 61 emerging contaminants (industrial chemicals,
8
pharmaceuticals & PCPs, drugs TPs & cathine, plant protection products, PPPs TPs, stimulants TPs and naturally occurring compounds) have been detected in the analyzed samples. Furthermore, four sediment samples, two from Ukraine, one from Open Sea and one from Georgia were collected for monitoring the degree of contamination in sediments of the Black Sea. Among the seven screened phthalates, only Di (2-ethylhexyl) phthalate (DEHP) and Di-n-butyl-phthalate were detected in the samples and all screened phenols were below the detected limits in the tested samples. Fourteen ECs were detected in sediment samples and most of the detected compounds were plant protection products. Finally twenty biota samples were collected from Georgia, Ukraine and Russian Federation and analyzed in total. Among the eighteen PFCs that were screened in the biota samples, only Perfluoroctane sulfonic acid (PFOS) was detected in two fish from Georgia and two from Ukraine. Moreover, thirty six ECs were detected in the analyzed biota samples. The results indicate the presence of drugs TPs in Georgian (79.9%) and Ukrainian (72.2%) samples, whereas pharmaceutical and PCPs contribute the most (59.6%) to the total EPs pollution in the Russian Federation samples.
The aggregated target analysis results produced within EMBLAS II and EMBLAS plus projects, implemented in 2016-2017 and 2019, respectively were evaluated in this project. Apart from the determination of priority pollutants included in the WFD (2013/39/EC), unique data on the occurrence of emerging contaminants have been extracted for several seawater, biota samples and sediments, collected in coastal/shelf areas and open sea. The overall results indicate that the levels of specific contaminants or the selected sampling sites remarkably affect the overall pollution pattern of the samples. To conclude both the number and the average total concentration of emerging contaminants were lower in 2019 samples compared to the previous campaigns.
Keywords:
Black Sea, Emerging Contaminants, High Resolution Mass Spectrometry, Marine Environment.
