A novel approach based on GC-Orbitrap-HRMS analysis for the simultaneous multi-class determination of priority and emerging contaminants in thermally processed paprika and almond

This study investigates the formation of process-induced contaminants across various thermal treatments in paprika (dried, sterilised and smoked) and almond (natural, roasted and fried). A total of 25 analytes were simultaneously determined. These included 15 PAHs, styrene, and anthraquinone, classified as contaminants by the International Agency for Research on Cancer (IARC)), alongside emerging thermal markers, specifically 6 furanones derivates, 1 pyranone derivative, and benzofuran. A novel multicompound analytical method based on ultrasound-assisted extraction coupled with gas chromatography and Orbitrap high-resolution mass spectrometry (UAE-GC-Orbitrap-HRMS) was developed and validated. The method demonstrated excellent linearity (0.1-200 μg/L), trueness (mean recovery values between 88.6% and 107.9%), acceptable intra and inter-day precision (RSDs < 11%) and negligible to moderate matrix effects (MEs ≤ ±50%). Notably, low limits of detection (LODs ranging from 0.05 to 0.08 μg/kg) and quantification (LOQ of 5 μg/kg) were achieved for both complex matrices. The results demonstrated that traditional smoking is the primary driver of PAHs contamination. Unlike non-smoked samples (< LOQ), smoked paprika reached maximum levels of 132.7 μg/kg (BaP) and 2201.8 μg/kg (∑PAH4). Anthraquinone and benzofuran were identified as exclusive markers of smoke exposure. In contrast, PAHs were not detected in almond, while furanones emerged as key indicators of thermal intensity. Roasting, more than frying, might promote furanone formation via dry-heat Maillard pathways and lipid degradation. These findings provide essential quantitative data on regulated and emerging contaminants, proving that high-resolution GC-Orbitrap is a superior tool for the comprehensive assessment of food safety in processed products.