Application of passive sampling devices for screening of micro-pollutants in marine aquaculture using LC–MS/MS

Knowledge on the presence of micro-pollutants, in particular emerging contaminants, such as pharmaceuticals, biocides or some pesticides, in semi-enclosed coastal areas, where fish farms are installed, is very limited. This article shows data on the presence of micro-pollutants over 1 year monitoring campaign carried out in a fish farm placed on the Mediterranean Sea. With this work, the results of the development of an analytical procedure which, makes use of passive sampling techniques (with polar organic chemical integrative samplers, POCIS, pharmaceutical configuration) and of the LC–QLIT-MS system, are presented. The development of the analytical procedure entail laboratory-based calibration with the samplers POCIS, for calculating uptake rates and sampling rates of compounds representative of a wide range of polarity (4.56 ≥ log Kow ≥ −0.12). The uptake of the target compounds in the sampler POCIS, follows a linear pattern for most compounds, and sampling rates varied from 0.001 to 0.319 l/d. The calibration experiments have shown that POCIS pharmaceutical configuration could be used for sampling other non-target compounds, such as pesticides and biocides with a log Kow ≤ 4. The sampling rates for each selected compound were obtained using spiked seawater for further estimation of time-weighted average (TWA) concentration of micro-pollutants in the water column, during the field study. An analytical method was developed with the LC–QLIT-MS system and validated to ensure a satisfactory performance for the detection of the target micro-pollutants in water. The limits of detection (LODs) achieved were between 0.01 and 1.50 μg/l. During the monitoring campaign, among the selected compounds, metronidazole, erythromycin, simazine, atrazine, diuron, terbutryn, irgarol, trimethoprim, carbaryl, flumequine, TCMTB and diphenyl sulphone (DPS) were detected. Most of target compounds found were at average concentrations which ranged from 0.01 to 75 ng/l. Irgarol, simazine, diuron, atrazine and DPS were the micro-pollutants most frequently detected over the period of the monitoring programme carried out.