Development and Comprehensive Diverse-Matrix Evaluation of Four PAHs Using Solvent-Modified QuEChERS-GC-MS with Freeze-Out

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are recognized carcinogens that enter the food chain through pre-existing environmental contamination (air, water, soil), and their formation and accumulation during food preparation and processing involve high temperatures. We established a modified QuEChERS GC-MS method that couples n-hexane-saturated acetonitrile containing 1% toluene with a freeze-out step. Compared to the previously reported ACN QuEChERS protocol, this method enhanced PAH desorption and suppressed lipid interference across four matrices. The method linearity (R2 >= 0.99), limit of detection (LOD, from 0.03 to 0.20 mu g/kg), limit of quantitation (LOQ, from 0.10 to 0.60 mu g/kg), and intra-/inter-day precision (<= 5.7% RSD) all satisfied AOAC criteria. The modified QuEChERS reduced solvent consumption and shortened preparation time compared to other conventional extraction methods. The developed method was applied to 302 retail food samples, and Kezuribushi was found to have the highest concentration of the 4PAHs, reaching 22.0 mu g/kg. Risk assessment based on EFSA's margin-of-exposure (MOE) approach identified grilled chicken feet (MOE = 7604) as a potential health concern, as this value falls below EFSA's threshold of 10,000 for potential risk characterization. The validated method enables sensitive and scalable monitoring of PAHs in complex food matrices within the tested matrices and conditions.