陈湘颖, 曾铭, 阿文伟, 范莹颖, 曾莹, 陈燕芬, 李丹, 钟怀宁, 郑建国. 气相色谱-质谱法测定食品接触材料及制品中4种癸二酸酯类化合物迁移量[J]. 质谱学报, 2024, 45(4): 558-566. DOI: 10.7538/zpxb.2024.0016
引用本文: 陈湘颖, 曾铭, 阿文伟, 范莹颖, 曾莹, 陈燕芬, 李丹, 钟怀宁, 郑建国. 气相色谱-质谱法测定食品接触材料及制品中4种癸二酸酯类化合物迁移量[J]. 质谱学报, 2024, 45(4): 558-566. DOI: 10.7538/zpxb.2024.0016
CHEN Xiang-ying, ZENG Ming, A Wen-wei, FAN Ying-ying, ZENG Ying, CHEN Yan-fen, LI Dan, ZHONG Huai-ning, ZHENG Jian-guo. Determination of Migration of Four Sebacic Acid Esters in Food Contact Materials and Products by Gas Chromatography-Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(4): 558-566. DOI: 10.7538/zpxb.2024.0016
Citation: CHEN Xiang-ying, ZENG Ming, A Wen-wei, FAN Ying-ying, ZENG Ying, CHEN Yan-fen, LI Dan, ZHONG Huai-ning, ZHENG Jian-guo. Determination of Migration of Four Sebacic Acid Esters in Food Contact Materials and Products by Gas Chromatography-Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(4): 558-566. DOI: 10.7538/zpxb.2024.0016

气相色谱-质谱法测定食品接触材料及制品中4种癸二酸酯类化合物迁移量

Determination of Migration of Four Sebacic Acid Esters in Food Contact Materials and Products by Gas Chromatography-Mass Spectrometry

  • 摘要: 本研究建立了气相色谱-质谱(GC-MS)法同时测定食品接触材料及制品中癸二酸二正丁酯、癸二酸二(2-乙基己基)酯、癸二酸二异辛酯和癸二酸二(2,2,6,6-四甲基-4-哌啶)酯等4种癸二酸酯类化合物在食品模拟物及化学替代溶剂中的迁移量。对于化学替代溶剂95%乙醇和异辛烷,采用直接液体进样法;对于橄榄油食品模拟物,用乙腈萃取后采用基质分散萃取净化后上机测试;对于其他食品模拟物(水、4%乙酸、10%乙醇、20%乙醇和50%乙醇),采用正己烷萃取后上机测试。在优化的实验条件下,4种化合物的分离效果良好,在0.30~5.0 mg/kg和0.50~5.0 mg/kg浓度范围内分别呈良好的线性关系,相关系数(r2)大于0.995;4种癸二酸酯类化合物迁移量的检出限和定量限分别为0.1~0.2、0.3~0.5 mg/kg。对塑料样品水、4%乙酸、10%乙醇、20%乙醇、50%乙醇、95%乙醇和异辛烷浸泡液进行0.30、2.0、4.0 mg/kg 3个浓度水平的添加实验,对橄榄油浸泡液进行0.50、2.0、4.0 mg/kg 3个浓度水平的添加实验,测得加标回收率在92.5%~108%之间,相对标准偏差(RSD)在2.4%~8.8%之间。本方法灵敏度高、精密度和准确度好,能够满足食品接触材料及制品中4种癸二酸酯类化合物迁移量的检测需求。

     

    Abstract: A method of gas chromatography-mass spectrometry (GC-MS) was established to determine the migration of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, decanedioic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester in water-based, acidic and alcoholic food simulants, and olive oil and chemical alternative solvents. The 95% ethanol and isooctane chemical substitution solutions were directly analyzed by GC-MS. The olive oil samples were extracted with acetonitrile followed by QuEChERS purification, and then analyzed by GC-MS. Other simulants (water, 4% acetic acid, 10% ethanol, 20% ethanol, and 50% ethanol) were extracted with n-hexane and then determined by GC-MS. The results showed that the method is well performed under optimized conditions, with the correlation coefficient (r2) greater than 0.995. The limits of detection and the limits of quantitation of the four sebacic acid ester compounds in water, 4% acetic acid, 10% ethanol, 20% ethanol, 50% ethanol, 95% ethanol, isooctane, and olive oil simulants are 0.1-0.2 mg/kg, 0.3-0.5 mg/kg, respectively. Migration experiments on plastic samples were conducted, and spiking experiments at three concentration levels of 0.30, 2.0, 4.0 mg/kg in water, 4% acetic acid, 10% ethanol, 20% ethanol, 50% ethanol, 95% ethanol, and isooctane food simulants, and three concentration levels of 0.50, 2.0, 4.0 mg/kg in olive oil food simulants were carried out. The spiking recoveries range from 92.5% to 108%, and the relative standard deviations (RSDs) are 2.4%-8.8%. The method solves the problem that decanedioic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester cannot be extracted into n-hexane in 4% acetic acid by adjusting pH value using ammonium hydroxide, the optimal pH range was determined by comparing the responses of four targets at different pH values. QuEChERS was firstly used for migration experiments of sebacic acid esters in food contact materials to solve the turbidity and partial oil precipitation of olive oil simulants in the concentration process after extraction. By optimizing the QuEChERS filling material, the interference of organic acids, fatty acids, sugar and other impurities on the targets were reduced, producing greater separation effect of the targets. The separation efficiency of four chromatographic columns with different polarity was compared, and the DB-17HT column was selected to detect the four sebacic acid esters simultaneously. Plastics such as polypropylene, polyethylene terephthalic acid terephthalate, polyvinyl chloride, composite membranes, paper cups, recycled PET and recycled PVC were collected and migration experiments were carried out, the migration of sebacic acid esters in these plastics materials was investigated. This method is highly sensitive, precise, and accurate, fully meeting the requirement for determining the migration of the sebacic acid esters in food contact materials and their products.

     

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