Coupling solid-phase microextraction and high-performance liquid chromatography for direct and sensitive determination of halogenated fungicides in wine

A solid-phase microextraction (SPME) method coupled to high-performance liquid chromatography with diode array detection (HPLC–DAD) for the analysis of six organochlorine fungicides (nuarimol, triadimenol, triadimefon, folpet, vinclozolin and penconazole) in wine was developed. For this purpose, polydimethylsiloxane–divinylbenzene-coated fibers were utilized and all factors affecting throughput, precision, and accuracy of the SPME method were investigated and optimized. These factors include: matrix influence, extraction and desorption time, percentage of ethanol, pH, salt effect and desorption mode. The performed analytical procedure showed detectability ranging from 4 to 27 μg l−1 and precision from 2.4 to 14.2% (as intra-day relative standard deviation, RSD) and 4.7–25.7% (as inter-day RSD) depending on the fungicide. The results demonstrate the suitability of the SPME–HPLC–DAD method to analyze these organochlorine fungicides in red wine.