关键词: 超高效液相色谱, 聚乙烯, 添加剂, 食品接触材料

Abstract:

Measurement of additive residues in food contact materials is important for safety monitoring at the initial stage. Most of the current studies focus on the determination of the migration amounts of chemical hazards from food contact materials into food simulants. Studies on chemical hazard residues in food contact materials are limited to monomers, oligomers, heavy metals, phthalic acid esters, and biphenols, which are known environmental pollutants. Only a few studies have investigated analysis methods for additive residues in food contact materials. In this study, the main factors (monitoring wavelength, chromatographic column, mobile phase, extraction solvent, etc.) that affect the accuracy and sensitivity of eight compounds, including three antioxidants, three light stabilizers, and two plasticizers, were investigated during sample preparation and instrument analysis. A method based on ultrahigh-performance liquid chromatography (UPLC) was developed for the simultaneous determination of these eight additives in polyethylene (PE). The PE food contact material sample was ground to homogenize the particle sizes under freeze-grinding. After comparing the extraction efficiencies of methylbenzene, chloroform, acetone, and acetonitrile, 2.0 g of the sample was extracted with methylbenzene at 80 ℃ and 10.34-11.72 MPa (1500-1700 psi) by accelerated solvent extraction (ASE) for 10 min once. The exaction solvent (10 mL) was transferred and concentrated to near dryness under a gentle stream of nitrogen gas and then re-dissolved in 10 mL of the initial mobile phase (70% (v/v) methanol in water). Finally, the eight compounds were analyzed by UPLC. After optimization of the analytical column and mobile phases, the eight analytes were separated on an ACQUITY UPLC BEH C₈ chromatographic column (100 mm×2.1 mm, 1.7 μm) by gradient elution using water and acetonitrile as the mobile phases. The column oven temperature, flow rate of the mobile phase, and injection volume were 30 ℃, 0.3 mL/min, and 5 μL, respectively. The analytes were detected by a diode assay detector (DAD) in the scanning range of 210 nm to 400 nm. The monitoring wavelength was set at 230 nm, 250 nm, 280 nm, and 330 nm. External standard calibration curves were used for quantification. Under the optimized conditions, the calibration curves for the eight compounds showed good linearity in the range of 0.2 μg/mL to 10 μg/mL, and the correlation coefficients were >0.999. The recoveries in spiked blank polyethylene samples at the level of 0.05% were in the range of 83.8% to 103.4%, with relative standard deviations (RSDs) ranging from 0.14% to 7.86%. To validate the method, PE reference materials containing these eight compounds were manufactured at the content level of 0.2% to 0.9%. The recoveries using the prepared reference materials ranged from 63.5% to 118.5%, and the RSDs were in the range of 4.61% to 15.6%. The limits of detection (LODs, S/N=3) of all the eight compounds were 0.005% and the limits of quantification (LOQs, S/N=10) were 0.02%, in compliance with the current legislation. To assess the feasibility and potential of the proposed approach for routine analyses of these eight compounds, the developed method was applied to the analysis of these compounds in ten PE food packages and PE gloves. In six samples, tris(2,4-di-tert-butylphenyl)phosphite (Irganox 168) was detected at a level of 0.02%-0.07%, which was lower than the maximum level of this compound in PE food contact material products regulated in GB 9685-2016 at 0.2%. The method is compliant with the current legislation, and it can be used for the monitoring and supervision of these eight additives in PE food contact materials.

Key words: ultrahigh-performance liquid chromatography (UPLC), polyethylene (PE), additive, food contact material