Green microextraction and GC × GC/MS quantification of PAHs and derivatives in roasted/smoked spices and dry herbs: implications for food safety.

This study presents a green, cost-effective analytical method for the determination of polycyclic aromatic hydrocarbons (PAHs) and their derivatives in roasted and smoked spices and dry herbs, combining hydrophilic microporous cartridge direct immersion solid-phase microextraction (HMCart-DI-SPME) with comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC/MS). The novel HMCart-DI-SPME technique simplified sample preparation while enhancing extraction efficiency, and its optimization via Doehlert experimental design ensured high precision, linearity, and sensitivity. The method demonstrated excellent analytical performance, with precision (RSD) < 13 %, linearity coefficients (R2) >0.93, and recoveries ranging from 87.5 % to 108.5 %. High sensitivity was confirmed by limits of detection (LOD) and quantification (LOQ) ranging from 0.09 to 0.88 μg kg-1 and from 0.27 to 2.67 μg kg-1 respectively. These results underscore the method's suitability for determining trace levels of PAHs in complex food matrices. The method was employed to analyze commercial samples, revealing that while most exhibited toxicologically acceptable PAH levels, cumulative exposure risks depended on consumption frequency. Risk assessment via Margin of Exposure (MOE) and Incremental Lifetime Cancer Risk (ILCR) identified smoke powder (ILCR = 1.07 × 10-4) as a high-risk product, with smoked paprika and black pepper also requiring monitoring. These findings emphasize stricter spice safety controls and present a robust, sustainable method for contaminant monitoring in complex matrices.