Sequential thin film-solid phase microextraction as a new strategy for addressing displacement and saturation effects in food analysis.

Solid-phase microextraction (SPME) is robust, selective, sensitive, and can be automated. However, low extraction phase to sample volume ratio sometimes results in saturation, competition, or swelling phenomena in complex samples. A sequential extraction method using two thin-film SPME (TF-SPME) devices with different selectivities was developed. The sequential application of the thin films provided higher extraction capacities, while avoiding swelling, saturation, and displacement effects, and enabled the quantitative determination of all compounds in the analyzed samples, independent of their polarity and affinity to extraction phases. In the first step, a TF-SPME device with a poly(dimethylsiloxane) (PDMS) coating was used to deplete non-polar and other compounds present at high concentrations in the sample, which are typically associated with the undesirable phenomena. In the second step, a TF-SPME device coated with a combination of hydrophobic/lipophilic balanced (HLB) particles and PDMS (HLB/PDMS) was applied for the direct microextraction of the remaining compounds, including polar compounds left over after the first step. The proposed method resulted in decreased levels of interference and yielded encouraging analytical data for beer samples.