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1 4 3 Vol. 4 No Journal of Food Safety and Quality Jun., 徐幸 *, 杨卫花, 赵浩军, 张燕, 彭飞进 (, ) 摘要 : 目的 17 -, 方法, - 结果 5~10000 μg/l, 0.999, 0.1~25 μg/l, 0.001~0.1 mg/kg 3 ( mg/kg) 83.7% 105.9%, (RSD, n=6) 1.9% 5.7% 结论, 关键词 : -; ; ; Determination of 17 phthalate esters in different wines and liquors by gas chromatography-tandem mass spectrometry XU Xing *, YANG Wei-Hua, ZHAO Hao-Jun, ZHANG Yan, PENG Fei-Jin (Dali Quality and Technical Supervision Comprehensive Inspection Centre, Dali , China) ABSTRACT: Objective To establish a method for the determination of 17 phthalate esters (PAEs) in different types of wine by gas chromatography-tandem mass spectrometry (GC-MS/MS). PAEs content distribution of different types of wine on the market had been analyzed. Methods The samples were extracted with hexane, and were detected by GC-MS/MS. Results The linear range of detection was from 5 to μg/l (R>0.999). The detection limits of machine of 17 PAEs were 0.1 to 25 μg/l and those in the samples were to 0.1 mg/kg. The average recoveries of three concentrations (0.3, 3.0, 30.0 mg/kg) were ranged between 83.7% and 105.9%, and the relative standard deviations (RSD, n = 6) were ranged between 1.9% and 5.7%. There were more PAEs in compound wine than in other types of liquor. Conclusion This method is highly sensitive, accurate and reproducible, and it is suitable for the detection of PAEs in liquor. KEY WORDS: gas chromatography-tandem mass spectrometry; phthalate acid esters (PAEs); plasticizer; alcohol food 1 引言 (phthalate acid esters, PAEs), [1] PAEs, PAEs, * 通讯作者 :,, @qq.com *Corresponding author: XU Xing, Engineer, Dali Quality and Technical Supervision Comprehensive Inspection Centre, No.1 Mailbox, Economic Development Zone, Dali , China @qq.com

2 878 4, ; PAEs, [2-4] PAEs [5], PAEs, PAEs [6] , (α-)(dehp) (DINP) (DBP) mg/kg 0.3 mg/kg GB/T [7], 16 [8,9] ; Huang [10] (VSBME) ; Russo [11] (SPE) ; Lee [12] (DI-SPME) ; [13,14] 16 ; [15] - 18 DINP,,, 2 材料与方法 2.1 仪器与试剂 Agilent 7890 ( ); Agilent 7000A, EI( )( ); AB204-E ( - ); MTN-2800W ( ); ( ) (, ) 17 PAEs : (2- ) ( ) (2- ) (2- ) (2- ), 1000 mg/l, 2.2 定量工作曲线 100 ml, 10 mg/l, μg/l,, 2.3 样品处理 2 g ( g) 10 ml,, 10 ml,, 2.4 测定条件 气相色谱条件 DB-5MS ( 30 m 0.25 mm, 0.25 μm) ; He, 1.2 ml/min; : 60 (1 min), 20 /min 220, 5 /min 265, 10 /min 285 (3 min), 23 min;, 270 ;, 1 μl( ) 质谱条件 EI 230 ; 70 ev; 1.2 amu; 7 min; 285 ; 10-5 Pa 3 结果 3.1 质谱多重反应监测条件优化,, 50~300 amu, NIST,,,,, 2, (MRM) 1 1 MRM 17 PAEs, ( 1), DINP [16], 16,

3 3, : Table 1 表 1 多重反应监测的条件 Multiple reaction monitoring conditions (min) (amu) 1 (amu) 2 (amu) (ev) 1 DMP DEP DIBP DBP (2- ) DMEP ( ) BMPP (2- ) DEEP DPP DHXP BBP (2- ) DBEP DCHP (2- ) DEHP DPhP DNOP DINP DNP (MRM) (4.0 mg/l) Fig. 1 MRM chromatogram of standard solution of 17 PAEs (4.0 mg/l) : 1.DMP; 2.DEP; 3.DIBP; 4.DBP; 5.DMEP; 6.BMPP; 7.DEEP; 8.DPP; 9.DHXP; 10.BBP; 11.DBEP; 12.DCHP; 13.DEHP; 14.DPhP; 15.DNOP; 16.DINP; 17.DNP 3.2 方法的回收率与检出限 MassHunter, MassHunter, mg/kg, 6,, 2

4 酒类食品中邻苯二甲酸酯的分布情况 PAEs, 84 PAEs, DMP DIBP DBP BBP DEHP DINP 6 PAEs, DBP; (0.3 mg/kg) 15, 17.9%, 1.57 mg/kg, 5 ;, 9 DBP, DBP, 10.7%; PAEs 3, (MRM) 2 Table 2 表 2 检出限 回收率与相对标准偏差 Limits of detection, recovery and relative standard deviation R (μg/l) (mg/kg) (%) (RSD, n=6, %) 0.3 (mg/kg) 3.0 (mg/kg) 30.0 (mg/kg) DMP DEP DIBP DBP DMEP BMPP DEEP DPP DHXP BBP DBEP DCHP DEHP DPhP DNOP DINP DNP Table 3 表 3 不同酒类样品中 PAEs 的分布 Distribution of PAEs in the samples of different wines (mg/kg) DMP DIBP DBP BBP DEHP DINP

5 3, : (MRM) Fig. 2 MRM chromatogram of compound wine sample 4 讨论 GC-MS/MS, 17 PAEs, PAEs, PAEs,, PAEs [17],,, PAEs DIBP, PAEs 4, DMP DIBP DIOP [18], PAEs PAEs 参考文献 [1],,,. - [J]., 2012, 33(24): Ma YH, Ding HY, Ma L, et al. A quantitative structure-retention relationship study for prediction of GC retention times of phthalate esters [J]. Food Sci, 2012, 33(24): [2] Adibi JJ, Perera FP, Jedrychowski W, et al. Prenatal exposures to phthalates among women in New York City and Krakow [J]. Environ Health Persp, 2003, 111(14): [3] Yano K, Hirosawa N, Sakamoto Y, et al. Phthalate levels in baby milk powders sold in several countries [J]. B Environ Contam Tox, 2005, 74: [4] Agarwal DK, Lawrence WH, Autian J. Antifertility and mutagenic effects in mice from parenteral administration of di-2-ethylhexyl phthalate(dehp) [J]. J Toxicol Env Health, 1985, 16(1): [5],,,. [J]., 2010, 6: Xiao NY, Lu XC, Guo QB, et al. Research progress of phthalate plasticizer migration in plastic food packaging [J]. Packag Eng, 2010, 6: [6],. [J]., 2008, 18 (6): Chen J, Liu Y. Determination of PAEs in PVC packing materials by GC/MS with accelerated solvent extraction [J]. Inspection Quarantine Sci, 2008, 18 (6): [7] GB/T [S]. GB/T Determination of phthalate esters in foods[s]. [8]. GC-MS [J]., 2010, 19(6): Shao DL. Determination of phthalate esters residues in white spirit by GC-MS [J]. Chem Anal Meterage, 2010, 19(6): [9],,,. [J]., 2013, 2: Li CY, Zhang XL, Rao J, et al. Selection and optimization of the measurement method of phthalate esters in liquor [J]. Liquor Mak Sci Technol, 2013, 2: [10] Huang GL, Li HF, Zhang BT, et al. Vortex solvent bar microex-

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