Determination of fungicides in natural waters using solid-phase microextraction and gas chromatography coupled with electron-capture and mass spectrometric detection

This study develops a method for the analysis of seven fungicides in environmental waters, using solid-phase microextraction (SPME). The analyzed compounds — dicloran, chlorothalonil, vinclozolin, dichlofluanid, captan, folpet and captafol — belong to different classes of chemical compound (chloroanilines, sulphamides, phthalimides and oxazolidines) and are used mainly in agriculture and as antifouling paints. Their determination was carried out by gas chromatography with electron-capture and mass spectrometric detection. To perform SPME, four types of fibre have been assayed and compared: polyacrylate (85 μm), polydimethylsiloxane (100 and 30 μm), carbowax–divinylbenzene (CW–DVB 65 μm) and polydimethylsiloxane–divinylbenzene (65 μm). The main parameters affecting the SPME process such as pH, salt additives, methanol content, memory effect, stirring rate and adsorption–time profile were studied. The method was developed using spiked natural waters such as ground water, sea water, river water and lake water in a concentration range of 0.1–10 μg/l. Limits of detection of studied compounds were determined in the range of 1–60 ng/l, by using electron-capture and mass spectrometric detectors. The recoveries of all fungicides were in relatively high levels (70.0–124.4%) and the average R2 values of the calibration curves were above 0.990 for all the analytes. The SPME conditions were finally optimized in order to obtain the maximum sensitivity. The potential of the proposed method was realized by applying it to the trace-level screening determination of fungicides and antifouling compounds in sea water samples originating from various Greek marinas.