The solid-phase microextraction (SPME), invented by Pawliszyn in 1989, today has a renewed and growing use and interest in the scientific community with fourteen techniques currently available on the market. The miniaturization of traditional sample preparation devices fulfills the new request of an environmental friendly analytical chemistry. The recent upswing of these solid-phase microextraction technologies has brought new availability and range of robotic automation. The microextraction solutions propose today on the market can cover a wide variety of analytical fields and applications. This review reports on the state-of-the-art innovative solid-phase microextraction techniques, especially those used for chromatographic separation and mass-spectrometric detection, given the recent improvements in availability and range of automation techniques. The progressively implemented solid-phase microextraction techniques and related automated commercially available devices are classified and described to offer a valuable tool to summarize their potential combinations to face all the laboratories requirements in terms of analytical applications, robustness, sensitivity, and throughput.
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