Simultaneous determination of 76 micropollutants in water samples by headspace solid phase microextraction and gas chromatography-mass spectrometry

Abstract

This study focuses on the development of an analytical method based on headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 76 micropollutants in water samples. The selected micropollutants include volatile organic compounds (VOCs) (e.g. chlorobenzenes, chloroalkanes), endocrine disrupting compounds (EDCs) (e.g. bisphenol A and tributyl phosphate), odour compounds (e.g. limonene, phenol), fragrance allergens (e.g. geraniol, eugenol) and some pesticides (e.g. heptachlor, terbutryn). The experimental conditions affecting their extraction, such as the type of fibre, temperature and time of extraction, sample volume and ionic strength of the samples were optimized using HS-SPME. The method showed good linear range, reproducibility between days, repeatability and low detection limits (at ng L(-1) levels). The validated method has been applied to determine the target organic micropollutants in aqueous samples from different experimental research units of surface water, sea water, waste water and those effluents of advance membrane treatments. The optimized method showed good performance in the different types of samples studied. The analysis revealed the presence of several micropollutants at concentrations between 20 and 5000 μg L(-1), such as ethylbenzene, o-xylene, p-isopropilbenzene, D-limonene, citral and isoeugenol, due to the fact that these species are commonly used in domestic and industrial applications.

Keywords: EDCs; EDSP; EPA; EQS; GC–MS; Gas chromatography–mass spectrometry; HS-SPME; LOD; LOQ; Organic micropollutants; PDMS; PDMS/DVB; PDMS/DVB/CAR; RO; SPE; Solid phase microextraction; UF; VOCs; Water samples; Water treatment; endocrine disrupting compounds; endocrine disruptor screening program; environmental protection agency; environmental quality standards; gas chromatography–mass spectrometry; headspace solid phase microextraction; limit of detection; limit of quantification; polydimethylsiloxane; polydimethylsiloxane/divinylbenzene; polydimethylsiloxane/divinylbenzene/carboxen; reverse osmosis; solid phase extraction; ultrafiltration; volatile organic compounds.