Abstract: | A new sampling technique, Headspace Sorptive Extraction (HSSE), is here applied for the first time to the headspace sampling of medicinal and aromatic plants. The analyte partition coefficient between HSSE‐PDMS stir bar and sample headspace (K1), the concentration factor (CF), the reproducibility, and the minimum recoverable amount were determined by analyzing standard solution of high volatility C5–C7 compounds with different polarities and structures (cyclohexane, propyl acetate, hexanal, 1‐hexen‐3‐ol, isoamyl acetate, and 2‐heptanol). Four aromatic and medicinal plants, viz. rosemary (Rosmarinus officinalis L.), sage (Salvia officinalis L.), thyme (Thymus vulgaris L.), and valerian (Valeriana officinalis L.) were analyzed by HSSE‐GC with PDMS stir bars, and their concentration capacity was compared with those of S‐HS and HS‐SPME with different fibers. HSSE showed very high concentration capability with both standard and real sample components. |