高效液相色谱-串联质谱法测定食品接触材料及制品中33种初级芳香胺的迁移量

建立了高效液相色谱-串联质谱（HPLC-MS/MS）法测定食品接触材料及制品中33种初级芳香胺的迁移量。根据食品特性以及食品与食品接触材料的接触特点，不同基质样品分别采用20%乙醇、50%乙醇和3%乙酸溶液作为食品模拟浸泡液进行迁移实验。迁移溶液以甲醇和0.05%甲酸水溶液为流动相，经五氟苯基色谱柱梯度洗脱，在电喷雾正离子模式下以动态多反应监测模式检测，外标法定量。33种初级芳香胺在20%乙醇、50%乙醇和3%乙酸（氨水调至pH 7.0）迁移溶液中的绝对基质效应分别为86.1%~97.3%、88.7%~104.0%和62.7%~81.3%，在各自线性范围内的线性关系良好（r>0.99），检出限和定量限分别为0.02~1.04 μg/kg和0.07~3.26 μg/kg。本方法的迁移实验针对性强、灵敏可靠，可实现食品接触材料及制品中初级芳香胺迁移量的准确测定。

Determination of the Migration of 33 Primary Aromatic Amines from Food Contact Materials and Articles by High-Performance Liquid Chromatography-Tandem Mass Spectrometry

The commonly used analytical techniques for the detection of primary aromatic amines (PAAs) in food contact materials (FCMs) include gas chromatography-mass spectrometry (GC-MS), capillary electrophoresis (CE), high-performance liquid chromatography (HPLC), HPLC-tandem mass spectrometry (HPLC-MS/MS), HPLC-high resolution mass spectrometry (HPLC-HRMS), etc. The migration of PAAs was determined in various types of FCMs using the above-mentioned techniques, such as laminated flexible packaging materials, polyamide cookware, plastic bags, and napkins. For the migration experiment, those methods generally adopted a single contact time and contact temperature, which may deviate from the migration amount occurred in the actualapplication. In contrast, European Union Directive (EU) No 10/2011 (annex Ⅲ) specified the time/temperature conditions for migration test of food simulants and plastics. Therefore, it is reliable to detect the migration of PAAs based on the expected food contact situations including food nature, contact time, and contact temperature for different types of FCMs. In this study, a method of high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed for the determination of the migration of 33 PAAs from FCMs and articles. 20% ethanol, 50% ethanol and 3% acetic acid solutions were used as food simulant solutions to simulate the hydrophilic, lipophilic and acidic food. For FCMs, such as disposable paper cups, colored plastic knives and forks, food bags, plastic milk bottles, pacifiers, etc., they were cut into rectangles with the side lengths of 0.5-1.0 cm. FCM samples of 5 g were weighed in a volumetric flask, and food simulant immersion solution of 100 mL was added. According to the physiochemical properties of the main ingredients in food and whether the FCMs and articles are expected to repeat contact with food, the conditions of food simulant solution and migration experiments were optimized. Chromatographic separation of the migration solution was performed on a Kinetex F5 column by a gradient elution of 0.05% formic acid-methanol solution. The detection was completed in positive electrospray ionization (ESI⁺) and scheduled multiple reaction monitoring (MRM) mode. The external standard method was used for quantitation. The absolute matrix effects (AMEs) of the 33 PAAs in the migration solution of 20% ethanol, 50% ethanol, and 3% acetic acid (pH 7.0) were 86.1%-97.3%, 88.7%-104.0%, and 62.7%-81.3%, respectively. Good linearity (r>0.99) was obtained within their respective linear ranges. The limits of detection (LODs) and quantitation (LOQs) were 0.02-1.04 μg/kg and 0.07-3.26 μg/kg, respectively. This method is sensitive, reliable, and suitable for the accurate determination of the migration of PAAs from FCMs and articles.