Sample preparation is a very crucial step prior to sample analysis. Three green adsorptive sample preparation micro-extraction techniques were investigated (smart solid-phase microextraction (SPME), high-capacity sorptive extraction (HiSorb), and stir bar sorptive extraction (SBSE)) for the determination of volatile organic compounds (VOCs) emitted from vineyard soil samples after method optimization. More specifically, the 95 μm Carbon Wide Range/Polydimethylsiloxane (CWR/PDMS) smart SPME fiber, CWR/PDMS HiSorb, and PDMS Twister micro-extraction tools were compared for their extraction capabilities. The headspace (HS)-SPME-gas chromatography-mass spectrometry (GC–MS) method was proved better for the extraction of VOCs from the vineyard soils due to shorter exposure time (45 min), its automation (use of a fully automated system compared to the other two), and the high sample throughput analysis. The validation of the HS-SPME-GC–MS method showed good linearity (R2 ≥ 0.9951) and limit of detection (LOD), whereas the limit of quantitation (LOQ) ranged from 0.04-3.65 μg/kg. Also, the repeatability and reproducibility of the results showed a relative standard deviation (RSD) lower than 4.73 %. A total number of 47 soil-derived VOCs were identified through the validated HS-SPME-GC–MS method, and 9 targeted VOCs were quantified with total average concentrations ranging from 0.14-28.07 µg/kg. Smart SPME fiber proved beneficial over the two other tools, highlighting the aspects of green chemistry.
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