Effect of Transport Parameters and Device Geometry on Extraction Kinetics and Efficiency in Direct Immersion Solid-phase Microextraction.

An alternative strategy to increase mass transfer entails geometry optimization of the extraction systems including design of solid-phase microextraction (SPME) probes. In this work, a computational model was employed to elucidate practical aspects such as efficiency and kinetics of extraction by employing several new geometries. Extraction of a model analyte at static conditions with the configurations, such as thin-film, fiber, coated tip, and nanoparticles, was numerically simulated to obtain an in-depth understanding of the advantages and limitations of each geometry in microextraction and exhaustive modes. The attained results associated with the equilibration time dependency on shape were in good agreement with previously reported experimental observations. They demonstrate that the mass-transfer is highly dependent on the size and shape of the coatings and increases with a decrease in size of the devices particularly rapidly below 10 μm caused by radial diffusion effect. Nevertheless, extractions performed using octadecyl-functionalized magnetic nanoparticles demonstrated that higher enrichment factors are achievable with the use of a fewer number of particles in comparison to factors achieved via exhaustive extraction, where a larger number of particles must be employed, confirming theoretical predictions. The conclusions reached are valid for any extraction method. The results obtained herein are very useful toward the design and optimization of future extraction technologies and approaches.