| Abstract: | Diffusion of the analytes across the diffusion boundary layers and subsequently through the fiber coatings determines the extraction kinetics of solid‐phase microextraction in aqueous matrices. Besides, the matrix effects can distort the behaviors of the analytes transferring across the diffusion boundary layers. However, these processes were always studied via certain simplification, which often left the mass transfer through the fiber coatings unconsidered and the matrix effects partially investigated. Herein, a comprehensive study on the mass transfer processes in direct immersion solid‐phase microextraction was presented. Under different agitation speeds, it was determined that the mass transfer coefficients across the diffusion boundary layers were three to six orders larger than those through the fiber coatings. However, the mass transfer across the diffusion boundary layers was generally the major rate‐limiting step. In addition, the shuttle effect and the barrier effect, which were responsible for accelerating and retarding the extraction kinetics, respectively, were found to be the dominant matrix effect alternately under different agitation speeds. This study comprehensively illustrated the major rate‐limiting step and the dominant matrix effects through recording the mass transfer coefficients. |
