Processing-Dependent Acrylamide Formation in French Fries: Optimisation of QuEChERS-Based Extraction and HPLC-PDA Determination

Acrylamide is a thermally induced process contaminant formed predominantly through Maillard-type reactions in carbohydrate-rich foods and is considered a major food safety concern due to its potential genotoxic and carcinogenic properties. In the present study, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe)-based extraction and clean-up procedure followed by high-performance liquid chromatography coupled with photodiode array detection (HPLC-PDA) analysis was developed and optimised for the determination of acrylamide in French fries. Different clean-up strategies involving primary secondary amine (PSA), C18, and salt-assisted extraction systems were comparatively evaluated to improve analytical selectivity and chromatographic performance in complex potato matrices. The optimised procedure demonstrated satisfactory analytical performance and chromatographic selectivity for acrylamide analysis in thermally processed potato matrices, with an LOQ value of 32.3 µg kg−1, recoveries ranging from 79.4 to 86.6%, and relative standard deviation (RSD) values below 8%. The validated method was subsequently applied to investigate the influence of thermal processing conditions on acrylamide formation in frozen French fries processed using sunflower oil, riviera olive oil, and palm oil. Deep-fat frying formed substantially higher acrylamide concentrations (526.7–829.6 µg kg−1) than oven baking (285.5–480.6 µg kg−1) and air frying (272.1–673.6 µg kg−1), whereas repeated frying cycles markedly enhanced acrylamide formation, particularly in sunflower oil systems. The proposed analytical strategy offers a reliable and analytically robust approach for acrylamide determination while providing mechanistic insights into processing-dependent chemical transformations associated with acrylamide formation in potato-based foods.