Vacuum-assisted headspace thin-film microextraction: Theoretical formulation and method optimization for the extraction of polycyclic aromatic hydrocarbons from water samples

The thin films used in headspace thin-film microextraction (HS-TFME) enable higher sensitivity and superior extraction rates compared to other microextraction approaches, largely due to their greater surface area-to-volume ratio and extraction-phase volume. Nonetheless, analytes exhibiting a low affinity for the headspace and/or large partitioning between the extraction phase and headspace will still require more time to reach equilibrium. In this paper, we detail the development of a new method, termed as vacuum-assisted HS-TFME (Vac-HS-TFME), and we demonstrate how its use of vacuum conditions can accelerate the extraction kinetics of analytes with long equilibration times. The pressure-dependence of the extraction process was formulated and related to improvements in gas-phase diffusivity when lowering the total pressure. Four low-molecular-weight polycyclic aromatic hydrocarbons (PAHs) were used to experimentally verify the improvements in extraction efficiencies enabled by Vac-HS-TFME (vs. HS-TFME). To this end, the effects of temperature and extraction time on Vac-HS-TFME were investigated, with the results being compared to those obtained via regular HS-TFME. Furthermore, the use of a high-capacity sorbent in TFME allowed the positive effects of temperature and vacuum conditions to be combined successfully. Extraction-time profiles constructed at 30 and 50 °C revealed substantial acceleration in the overall extraction kinetics when sampling under vacuum conditions. At 50 °C, all of the analytes extracted via Vac-HS-TFME reached equilibrium within 45 min, whereas only two reached this state under atmospheric pressure. Vac-HS-TFME's analytical performance was evaluated under optimized conditions, and the results were compared to those obtained with regular HS-TFME. The findings revealed that for the two lighter PAHs, the performance of the two methods was similar since they were extracted close or at equilibrium. However, the calibration models for the two heavier PAHs tested here were linear over a wider concentration range (50-10000 ng L-1) when using Vac-HS-TFME, had superior intra-day repeatability (7.4% and 6.7% vs. 11% and 9.3% with regular HS-TFME), and the limits of detection were lower compared to regular HS-TFME (15 and 11 ng L-1 compared to 136 to 100 ng L-1 with regular HS-TFME). Finally, the analysis of spiked wastewater effluent samples showed that the matrix did not affect extraction. The proposed Vac-HS-TFME approach combines the advantages of low-pressure sampling and high-capacity sorbent, and has a great potential for future applications in food, flavour, environmental, and biological analyses.