Development of an analytical methodology for the determination of organochlorine pesticides by ethylene-vinyl acetate passive samplers in marine surface waters based on ultrasound-assisted solvent extraction followed with headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry

Abstract

A novel strategy for the analysis of 20 organochlorine pesticides (OCPs) monitoring in marine surface waters through ethylenevinyl acetate (EVA) passive samplers was developed and validated. The approach is based on the coupled of ultrasound-assisted solvent extraction (UASE) and headspace solid-phase microextraction (HS-SPME) as extraction method for OCPs from EVA samplers. The UASE-HS-SPME method was optimized with a 27-4 Plackett-Burman design, while the significant factors (salting out, temperature and extraction time) were optimized using a central composite design (CCD) combined with desirability function (DF). The OCPs detection was performed using multiple reaction monitoring (MRM) by gas chromatography-tandem mass spectrometry (GC-MS/MS). The optimum experimental conditions comprised: salting out: 23% wv-1 NaCl, temperature: 75°C and extraction time: 55 min. The optimized method was validated in terms of linearity (R2>0.9946), recovery (>61%) and inter-day and intra-day reproducibility (<19%) for 20 OCPs studied. The limits of detection (LODs) were ranging from 0.01 ng for α-hexachlorocyclohexane and 0.27 ng for endrin aldehyde. Finally, the methodology was tested in marine surface seawater of Southern Chile using EVA samplers, where twelve OCPs were detected at ultra-trace levels (ngL-1).