Analysis of volatile contaminants in vegetable oils by headspace solid-phase microextraction with Carboxen-based fibres

The headspace solid-phase microextraction (HS-SPME) efficiencies from vegetable oil of the recently available Carboxen–poly(dimethylsiloxane) (PDMS) and divinylbenzene–Carboxen–PDMS fibres were found to be much greater than those of the PDMS fibre for a number of volatile contaminants. Using these Carboxen-based fibres, the commonly used HS-SPME equilibration times for aqueous matrices of 30–45 min at room temperature for a number of halogenated and aromatic analytes with volatilities ranging from 1,1-dichloroethylene to hexachlorobenzene were found to be insufficient for the effective extraction of the less volatile analytes from vegetable oil. HS-SPME at 100°C for 45 min, followed by rapid cooling to 0°C with a 10 min continuing extraction, however, significantly increased the SPME efficiencies for the less volatile analytes. Spiking solutions were prepared in vegetable oil instead of methanol as the latter was found to displace analytes from the Carboxen material. Using either of the Carboxen-based fibres and SPME at 100°C, all the target analytes could be determined at low or sub-μg kg−1 with repeatability ≤10%, even though an equilibrium SPME of the less volatile analytes was not achieved.