A simultaneous dispersive liquid-liquid microextraction and GC-MS determination of PCBs and PAHs in nature waters

Abstract

The subject of this study is polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) – super ecotoxicants and widely distributed organic pollutants in natural waters. Their danger lies in acute toxicity, cumulative action, and long-term effects on living organisms. The degree of water ecosystem pollution is assessed based on the levels of indicator compounds, with 16 PAHs and 7 PCBs. Assessing the levels of these super ecotoxicants when they are simultaneously present in natural waters is an urgent task of ecological monitoring in order to obtain reliable information about the pollution level of the water body. The aim of this study is to evaluate the possibility of dispersive liquid-liquid microextraction (DLLME) of PCBs and PAHs and GC-MS determination in natural waters in their simultaneous presence. To achieve the set goal, the peculiarities of simultaneous extraction and determination of PAHs and PCBs from natural waters were studied. The selected range of analyte concentrations was determined based on literature data on environmental monitoring and the maximum allowable concentrations (MAC) of the investigated components in natural waters. The similarity of the applied methods for extraction and detection of PAHs and PCBs allowed for the justification of the approach to selecting a universal sample preparation scheme for simultaneous extraction and GC-MS determination of both classes of analytes. The possibilities of modifications of DLLME extraction of PAHs and PCBs, differing in dispersion method and nature of the extractor, were studied in combination with chromatographic-mass spectrometric determination of the analytes. Simultaneous extraction of super-toxicants was achieved by applying DLLME with a binary dispersant – 500 μl acetone + 500 μl acetonitrile and 150 μl chloroform as the extractor. The chloroform extract after DLLME extraction of the analytes without re-dissolution was used for GC-MS determination of 16 PAHs and 7 PCBs on a specific 60 m long capillary column with a 5% polyarylene + 95% dimethylpolysiloxane stationary phase with gradual heating of the thermostat from 60 to 290°C. Using the selected ion monitoring (SIM) mode increased the reliability of component identification in matrices of natural waters. The possibility of mutual influence of ecotoxicants on their extraction in the presence of each other was studied. Dispersive liquid-liquid microextraction with a binary dispersant provided simultaneous extraction of analytes at a level of 80-97%. The proposed analysis scheme allowed for GC-MS determination of 16 PAHs and 7 PCBs in the presence of each other in natural waters over a wide range of concentrations (0.02-40 μg/L) with an accuracy of 7-18% (PAHs) and 11-18% (PCBs). The relative standard deviations of repeatability and reproducibility for PAHs were in the ranges of 3.1-6.5% and 4.3-7.7%, respectively, and for PCBs 2.8-5.3% and 3.4-6.0%.