Determination of Polycyclic Aromatic Hydrocarbons in Olive Oil Samples by Gas Chromatography Tandem Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants that may accumulate in olive oil during harvesting and processing. The main objective of this study was to determine the levels of the four indicator PAHs (PAH4) in 20 fresh olive oil samples collected directly from olive mills in the Drosia area of Chalkida, Greece. To achieve this, a gas chromatography–mass spectrometry (GC-MS) method was developed and validated according to the performance criteria of Commission Regulation (EU) 2023/915. A QuEChERS extraction followed by clean-up and GC-MS analysis in selected ion monitoring mode (SIM) was developed and validated. The described sample preparation and experimental workflow provided a four-fold concentration of the analytes. The method was applied to 20 olive oil samples (Megaritiki cultivar) collected from different local producers during the 2025 harvest. All validation parameters satisfied the regulatory requirements (square of the correlation coefficient R2 >0.995, limit of detection (LOD) 0.07–0.13 μg kg−1, recoveries 62%–113%, precision within acceptable HorRat limits). The sum of the four indicator PAHs (ΣPAH4) ranged from 2.22 to 6.71 μg kg−1 (mean 3.54 μg kg−1), and every sample complied with the EU limits of 2 μg kg−1 for benzo[a]pyrene and 10 μg kg−1 for ΣPAH4. Olive oil produced in this Greek olive-growing region under current good manufacturing practices shows very low PAH contamination and presents negligible risk to consumers. The validated GC-MS procedure, incorporating a four-fold concentration step, constitutes a reliable and practical tool for routine monitoring by quality control laboratories.