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Updated: Dec 28, 2025

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Determination of the mass transfer coefficients in direct immersion solid-phase microextraction
Jianqiao Xu1, Qingkun Hu1, Xiwen Liu1
1KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou, Guangdong, P.R. China.
This study reveals that analyte diffusion through fiber coatings and boundary layers controls solid-phase microextraction kinetics. Matrix effects, like shuttle and barrier effects, alternately influence extraction speed based on agitation.
Area of Science:
- Analytical Chemistry
- Separation Science
Background:
- Solid-phase microextraction (SPME) kinetics in aqueous samples are governed by analyte diffusion.
- Previous studies often oversimplified mass transfer and matrix effects in SPME.
- Understanding these processes is crucial for optimizing extraction efficiency.
Purpose of the Study:
- To comprehensively investigate mass transfer processes in direct immersion SPME.
- To identify the rate-limiting steps in SPME extraction kinetics.
- To elucidate the role and behavior of matrix effects under varying agitation.
Main Methods:
- Direct immersion solid-phase microextraction (DI-SPME) was employed.
- Mass transfer coefficients were measured across diffusion boundary layers and fiber coatings.
- Experiments were conducted under various agitation speeds.
Main Results:
- Mass transfer coefficients through fiber coatings were 3-6 orders of magnitude smaller than across boundary layers.
- Mass transfer across diffusion boundary layers was identified as the primary rate-limiting step.
- Shuttle and barrier effects emerged as dominant matrix effects, alternating with agitation speed.
Conclusions:
- The study provides a detailed understanding of rate-limiting steps in DI-SPME.
- It clarifies the dynamic influence of matrix effects on extraction kinetics.
- This research offers insights for optimizing SPME method development.
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