Calibrant Free Sampling and Enrichment with Solid-Phase Microextraction: Computational Simulation and Experimental Verification

Abstract

Despite the benefits of diffusion-based calibrant-free sampling based on solid-phase microextraction (SPME), this quantification approach is often underestimated due to an inadequate understanding of how extraction parameters influence the extracted amount and quantification of analytes. Currently, application of this approach for complex samples with binding matrix components is very limited. This study presents the development of a computational model that is used to identify the critical parameters for the diffusion-based sampling. Simulations are conducted under simultaneous variations in Mass transfer and adsorptive surface binding constants and the presence of a binding matrix component in the sample. The simulation results correlate well with previously reported experimental data and improve the predictions when compared to previously introduced semiempirical models. This work enhanced basic understanding of physical processes involved in analyte quantification with SPME, which is of benefit when performing experimental designs, particularly where traditional calibration methods are not suitable.