4 3 Vol. 4 No. 3 2013 6 Journal of Food Safety and Quality Jun., 2013-17 徐幸 *, 杨卫花, 赵浩军, 张燕, 彭飞进 (, 671000) 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 (0.3 3.0 30.0 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 671000, 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 10000 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 0.001 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 :,, E-mail: 318673124@qq.com *Corresponding author: XU Xing, Engineer, Dali Quality and Technical Supervision Comprehensive Inspection Centre, No.1 Mailbox, Economic Development Zone, Dali 671000, China. E-mail: 318673124@qq.com
878 4, ; PAEs, [2-4] PAEs [5], PAEs, PAEs [6] 2011 6 15 551, (α-)(dehp) (DINP) (DBP) 1.5 9.0 mg/kg 0.3 mg/kg GB/T 21911-2008 [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- ) (4- -2- ) (2- ) (2- ) (2- ), 1000 mg/l, 2.2 定量工作曲线 100 ml, 10 mg/l, 5 25 50 100 400 1000 4000 10000 μg/l,, 2.3 样品处理 2 g ( 0.001 g) 10 ml,, 10 ml,, 2.4 测定条件 2.4.1 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( ) 2.4.2 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, : - 17 879 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 7.973 194 163 135 0 25 2 DEP 8.835 177 149 121 10 10 3 DIBP 10.561 223 149 167 10 25 4 DBP 11.268 223 149 121 10 30 5 (2- ) DMEP 11.589 149 93 121 20 50 6 (4- -2- ) BMPP 12.276 167 149 121 10 10 7 (2- ) DEEP 12.580 149 93 121 10 40 8 DPP 12.928 237 149 219 5 25 9 DHXP 14.939 251 149 233 5 25 10 BBP 15.115 206 149 123 5 20 11 (2- ) DBEP 16.465 149 121 93 10 40 12 DCHP 17.125 167 149 121 10 10 13 (2- ) DEHP 17.316 167 149 121 10 10 14 DPhP 17.520 225 197 153 10 30 15 DNOP 19.520 279 149 93 10 30 16 DINP 20.728 149 93 121 20 40 17 DNP 21.686 293 149 121 10 40 1 17 (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, 3 0.3 3.0 30.0 mg/kg, 6,, 2
880 4 3.3 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 0.9999 0.3 0.002 89.6 3.8 91.7 4.4 101.7 4.8 DEP 0.9995 0.3 0.002 89.8 3.6 87.6 2.0 94.3 5.0 DIBP 0.9995 0.1 0.001 88.8 5.7 92.1 2.0 92.2 3.5 DBP 0.9998 0.3 0.002 85.4 4.7 92.4 2.4 91.5 3.4 DMEP 0.9996 25 0.1 92.9 3.6 93.7 2.4 100.3 3.7 BMPP 0.9992 0.3 0.002 92.7 1.9 91.5 1.9 103.4 4.8 DEEP 0.9997 25 0.1 95.0 4.5 91.9 2.2 101.9 4.4 DPP 0.9996 0.3 0.002 100.7 5.1 97.8 1.9 96.7 4.3 DHXP 0.9999 0.3 0.002 88.3 4.5 91.9 2.7 100.3 3.5 BBP 0.9998 0.3 0.002 91.9 4.2 97.0 4.2 103.4 3.8 DBEP 0.9997 25 0.1 90.2 4.9 85.9 2.0 87.5 1.9 DCHP 0.9996 0.5 0.003 105.9 2.9 93.0 2.2 100.9 3.3 DEHP 0.9997 0.1 0.001 85.3 4.8 90.7 4.2 94.8 1.9 DPhP 0.9999 0.3 0.002 83.7 2.0 91.6 3.8 95.6 3.3 DNOP 0.9999 0.5 0.003 90.4 4.9 96.6 4.5 103.7 4.3 DINP 0.9999 1 0.005 91.5 3.0 91.2 3.4 102.4 4.4 DNP 0.9996 0.3 0.002 95.4 4.1 95.3 4.3 101.7 4.5 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 0.14 0.18 0.14 0.05 0.03 0.02 0.07 0.08 0.12 0.34 0.48 0.08 0.11 0.07 0.09 0.01 0.01 0.07 0.03 0.16 0.20 0.10 0.10
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