Strategies for coupling solid-phase microextraction with mass spectrometry

• We review coupling solid-phase microextraction (SPME) with mass spectrometry (MS).
• Principles, developments and applications for techniques coupling SPME with MS.
• SPME coupled with MS integrates significant advantages of both techniques.
• We particularly emphasize SPME coupled with ambient MS (AMS).

Solid-phase microextraction (SPME) has experienced significant development since its introduction as a sample-pretreatment technique in the early 1990s. SPME is suitable for interfacing with chromatography and mass spectrometry (MS), but progress in coupling with chromatography has exceeded that with MS. In the past two decades, efforts have been made to couple SPME and MS with different applications in various research fields. Based on these previous studies, this review article summarizes historical developments, principles and operation, practical applications, and recent trends in SPME coupled with five types of MS: (1) electron-impact MS, (2) inductively-coupled plasma MS, (3) laser-desorption/ionization MS, (4) atmospheric-pressure ionization MS and (5) ambient MS (AMS). We particularly emphasize efforts on SPME coupled with AMS.