Microsoft Word 杜娟二校

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1 7 4 Vol. 7 No Journal of Food Safety and Quality Apr., 杜娟 *, 马娇, 赵文霞, 宋杰 (, ) 摘要 : 目的 - -(GC-MS) 16 方法,,, GC-MS (SIM), 结果 μg/kg, %~110.5%, 0.3%~12.7% ; %~108.3%, 0.6%~12.7% 50.0~ μg/kg, 0.999, μg/kg 结论, PAEs 关键词 : -; ; ; Determination of 16 kinds of phthalate esters in edible oils by gas chromatography-mass spectrometry with isotopic internal standards DU Juan *, MA Jiao, ZHAO Wen-Xia, SONG Jie (China National Food Quality & Safety Supervision and Inspection Center, Beijing , China) ABSTRACT: Objective To establish a method for determination of 16 kinds of phthalate esters (PAEs) in edible oils by gas chromatography-mass spectrometry (GC-MS) with isotopic dilution method. Methods The samples were dissolved with n-hexane and extracted with acetonitrile, and then purified by solid-phase column. Using GC-MS with selected ion monitoring (SIM), quantitative analysis was performed based upon isotopic internal method. Results The spiked recoveries at levels of 500.0, , μg/kg used soybean oil and butter samples as blank matrix were respectively in the range of 67.4%~110.5% and 60.5%~108.3%. The relative standard deviations (RSDs) were respectively in the range of 0.3%~12.7% and 0.6%~12.7%. The experimental results showed that 16 kinds of PAEs had good linear relations in the range of 50.0~ μg/kg, the correlation coefficients were better than 0.999, and the limits of detection (LODs) of 16 PAEs were μg/kg. Conclusion The sensitivity, precision and LOD can meet the requirements for the determination of the practical samples. This method can be used for the simultaneous detection of PAEs in edible oil samples. KEY WORDS: gas chromatography-mass spectrometry; phthalate esters; edible oil; isotopic dilution method * 通讯作者 :,, dujuanwenling@163.com *Corresponding author: DU Juan, Intermediate Engineer, China National Food Quality & Safety Supervision and Inspection Center, Beijing , China. dujuanwenling@163.com

2 引言 (phthalate esters, PAEs),,,,,, PAEs [1],, [2], 20% ~ 50% [3], PAEs, PAEs,,, PAEs,, PAEs, PAEs, [4],, PAEs [5], PAEs,,,, PAEs,, PAEs,,, [6] PAEs (gas chromatography, GC) [7] - (gas chromatography-mass spectrometry, GC-MS) [8] - (gas chromatography with tandem mass spectrometry, GC-MS/MS) [9] (high performance liquid chromatography, HPLC) [10] (liquid chromatography-mass spectrometry, LC-MS) [11] - (high performance liquid chromatography with tandem mass spectrometry, HPLC-MS/MS) [12], GB/T PAEs 1.5 mg/kg, [13], 0.5 mg/kg, ; (primary secondary amine, PSA),, PAEs [14] PAEs,,, - 16, 2 材料与方法 2.1 材料, 9, 试剂与仪器 16 (1000 μg /ml): (DMP)(DEP) (DIBP)(DBP) (2-) (DMEP) (4- -2 ) (BMPP) (2-) (DEEP) (DPP)(DHXP) (BBP) (2- ) (DBEP) (DCHP) (2- ) (DEHP)(DPHP) (DNOP)(DNP), 99%,, Accustandard 4 16 (100 μg/ml): D 4 - (D 4 -DMP) D 4 - (D 4 -DEP) D 4 -(D 4 -DIBP) D 4 - (D 4 -DBP) D 4 - (2-) (D 4 -DMEP) D 4 - ( ) (D 4 -BMPP) D 4 -(2-) (D 4 -DEEP) D 4 - (D 4 -DPP) D 4 - (D 4 -DHXP) D 4 - (D 4 -BBP) D 4 - (2-) (D 4 -DBEP) D 4 - (D 4 -DCHP) D 4 -(2- ) (D 4 -DEHP) D 4 - (D 4 -DPhP) D 4 - (D 4 -DNOP) D 4 - (D 4 -DNP), 95.0 %, Sigma 4 (, Honeywell ); 7890A-5975C / GC/MS( EI, Agilent ); BS224s ( Sartorius ); 80-2 ( 壇 ); Vortex-Genie2 ( Scientific Industries ) PSA (6 ml): 2.3 实验方法标准溶液的配制 16 (10 μg/ml):

3 4, : ml 16 (1000 μg/ml) 100 ml, 10 μg/ml 16 D 4 (10 μg /ml): D 4-16 ( 0.1 mg) 10 μg /ml, 18, 16 D 4 (1 μg /ml): 10 μg/ml D ml 10 ml,, 1.0 μg/ml, 4, 样品的前处理 (1) 0.5 g, 10 ml, 25 μl D 4 - (10 μg/ml), 1 ml, 1 min, 5 ml, 2 min, 20 min, 3000 r/min 3 min, 5 ml, 2, 40, 2 ml, (2) PSA (solid phase extraction, SPE) 5 ml 5 ml PSA SPE, ;, 5 ml 5 ml - (4:96, V:V), ml,, 2 ml,, GC-MS (3) ( ):,, 仪器分析条件 (1) DB-5MS (30 m 0.25 mm, 0.25 μm, J&W ) : 60, 1 min, 20 /min 220, 1 min, 5 /min 280, 10 min, 20 /min 300, 4 min (2) (EI); 70 ev; () 260 ; 1 μl; ( >99.999%); 280 ; (SIM) 1 3 GC-MS, 16 PAEs SIM 1~ mg/l PAEs ( 0.1 mg/l) 1 Table 1 表 1 16 种 PAEs 的保留时间和质谱碎片离子 Retention time and mass fragment ions of 16 kinds of PAEs (min) (m/z) (m/z) 1 (DMP) , 77, 194, (DEP) , 177, 105, (DIBP) , 223, 104, (DBP) , 223, 205, (2-) (DMEP) , 149, 104, ( ) (BMPP) , 167, 85, (2-) (DEEP) , 72, 149, 104, (DPP) , 237, 219, (DHXP) , 251, 104, (BBP) , 91, 206, (2-) (DBEP) , 101, 85, (DCHP) , 167, 249, (2- ) (DEHP) , 167, 279, (DPHP) , 77, 104, (DNOP) , 279, 104, (DNP) , 293, 167,

4 Table 2 表 2 16 种 PAEs 同位素内标保留时间和质谱碎片离子 Retention time and mass fragment ions of internal standards of 16 kinds of PAEs (min) (m/z) (m/z) 1 (D 4 -DMP) , 77, 198, (D 4 -DEP) , 181, 109, (D 4 -DIBP) , 227, 108, (D 4 -DBP) , 227, 209, (2-) (D 4 -DMEP) , 153, 108, ( ) (D 4 -BMPP) , 171, 85, (2-) (D 4 -DEEP) , 72, 153, 108, (D 4 -DPP) , 241, 223, (D 4 -DHXP) , 255, 108, (D 4 -BBP) , 91, 210, (2-) (D 4 -DBEP) , 105, 85, (D 4 -DCHP) , 171, 253, (2- ) (D 4 -DEHP) , 171, 283, (D 4 -DPHP) , 77, 108, (D 4 -DNOP) , 283, 108, (D 4 -DNP) , 297, 171, μg/l PAEs ( μg/l) Fig. 1 Total ion chromatogram of 16 kinds of PAEs with the concentration of μg/l(isotopic internal standards, μg/l) : 1.DMP(D 4 -DMP); 2.DEP(D 4 -DEP); 3.DIBP(D 4 -DIBP); 4.DBP(D 4 -DBP); 5.DMEP(D 4 -DMEP); 6.BMPP(D 4 -BMPP); 7.DEEP(D 4 -DEEP); 8.DPP(D 4 -DPP); 9.DHXP(D 4 -DHXP); 10.BBP(D 4 -BBP); 11.DBEP(D 4 -DBEP); 12.DCHP(D 4 -DCHP); 13.DEHP(D 4 -DEHP); 14.DPhP; 15.DNOP(D 4 -DNOP); 16. D 4 -DPhP; 17.DNP(D 4 -DNP).

5 4, : 结果与讨论 3.1 提取溶剂的选择 PAEs,, PAEs,, ; ( μg/kg),, 70%~110%,,,,,,,, 2 ml, 3.2 固相萃取 (SPE) 净化,,,, (gel permeation chromatography, GPC),,,, SPE,, [15], PSA,, 3.3 色谱条件的选择 PAEs, DNOP DNP,, DB-5MS 16 PAEs,, GC-MS,,, 3.3 ( 1) 3.4 方法学参数验证线性范围及方法检测限, 16 (10 μg/ml) μl 16 D 4 (1 μg/ml)125.0 μl, 1 ml, μg/l, μg/l, GC-MS, ( 3) PAEs 50.0~ μg/l, r (S/N) 3, μg/kg,, 16 PAEs (S/N) 3, μg/kg Table 3 表 3 16 种 PAEs 的线性方程相关系数及方法检测限 Linear equations, correlation coefficient (r) and limit of detection (LOQ) of 16 kinds of PAEs r LOD(μg/kg) 1 DMP Y=1.177X DEP Y=1.083X DIBP Y=1.081X DBP Y=1.062X DMEP Y=0.227X BMPP Y=2.704X DEEP Y=1.603X DPP Y=0.986X DHXP Y=1.007X BBP Y=1.059X DBEP Y=1.047X DCHP Y=0.944X DEHP Y=0.996X DPHP Y=2.301X DNOP Y=1.026X DNP Y=1.111X

6 方法的精密度和回收率, PAEs 3 ( μg/kg), 6, 16 D 4 (1 μg/ml)125.0 μl, μg/kg, (RSD),,, %~110.5%, RSD 12.7%, %~108.3%, RSD 12.7%, ( 4) 样品分析 ,, 90, PAEs,, PAEs, DBP DEHP, 14 PAEs, 5 DBP 1.74 mg/kg, DEHP 1.26mg/kg,, PE PP PAEs, ;, Table 4 表 4 大豆油和黄油 3 水平加标回收实验结果 (n=6) Recovery and relative standard deviations (RSDs) at 3 spiked level in soybean oil and butter (n=6) /(μg/kg) /% RSD/% /% RSD/% DMP DEP DAP DIBP DBP DMEP BMPP DEEP

7 4, : /(μg/kg) 续表 4 /% RSD/% /% RSD/% DPP DHXP BBP DBEP DCHP DEHP DPHP DNOP DNP Table 5 表 5 90 份油脂样品 16 种 PAEs 的检出情况 Results obtained for determination of 16 kinds of PAEs in 90 oil samples DBP/mg/kg ND ND ND~1.57 ND~1.74 ND~1.09 ND ND~1.37 ND ND /% DEHP/mg/kg ND~1.22 ND~1.26 ND ND ND ND ND~1.06 ND~1.11 ND /% : ND

1496 7 4 结论 16, GC-MS 16 PAEs,, 16 PAEs 50.0~1000.0 μg/l, r 0.999; 500.0 1000.0 2500.0 μg/kg, 16 60.5%~110.5%, RSD<12.7%, PAEs 参考文献 [1],,. - 18 [J]., 2013, 9(32): 40 45. Rong WG, Ruan H, Ma YJ.

8 结论 16, GC-MS 16 PAEs,, 16 PAEs 50.0~ μg/l, r 0.999; μg/kg, %~110.5%, RSD<12.7%, PAEs 参考文献 [1],, [J]., 2013, 9(32): Rong WG, Ruan H, Ma YJ. Determination of 18 phthalate acid esters in liquor and rice wine samples by gas chromatography-mass spectrometry [J]. Chin J Anal Lab, 2013, 9(32): [2],,,. [J]., 2014, (2): Peng LY, Wang WG, Wang X, et al. Rapid screening of trace phthalate estersin-wine using ion mobility spectrometry [J]. Chin J Anal Chem, 2014, (2): [3] Guart A, Bono-blay F, Borrell A, et al. Migration of plasticizers phthalates, bisphenol A and alkylphenols from plastic containers and evaluation of risk [J]. Food Addit Contam Part A Chem Anal Control Expo Risk Assess, 2011, 28(5): [4] Sorensen LK. Determination of phthalates in milk and milk products by liquid chromatography/tandem mass spectrometry [J]. Rapid Commun Mass Spectrom, 2006, 20(7): [5],,. [J]., 2013, (38), 1 4. Wang RY, Jin CZ, An J. The plasticizer and the safety of grain and oil products [J]. China Oils Fats, 2013, (38): 1 4. [6],, [J]., 2012, 40(3): Li T, Tang Z, Hong XW. Determination of 17 phthalate acid esters in fatty food by dispersive solid phase extraction-gas chromatography-mass spectrometry [J]. Chin J Anal Chem, 2012, 40(3): [7],,,. - [J]., 2006, 34(8): Li MX, Wu JH, Zeng W, et al. Determination of phthalate esters in water by single-drop micro extraction coupled with gas chromatography [J]. Chin J Anal Chem, 2006, 34(8): [8] 玥,,,. 16 GC-MS [J]., 2014, 29(2): Chu Y, Liang DP, Sun YM, et al. Determination of 16 phthalate acid esters in foods by gas chromatography-mass spectrometry [J]. J Chin Cereals Oils Assoc, 2014, 29(2): [9],,,. - - [J]., 2015, 37(5): Wang SJ, Lei W, Du XN, et al. Determination of phthalate ester residues in liquor by gas chromatography tandem triple quadruple mass spectrometry(gc-ms/ms) with isotopic internal standards [J]. Chemical Reagents, 2015, 37(5): [10],,,. [J]., 2008, 27(7): Zheng HH, Li J, Wu DN, et al. Determination of phthalates in cosmetic by ultra performance liquid chromatography [J]. Chin J Anal Lab, 2008, 27(7): [11] Chen XJ, Bester K. Determination of organic micro-pollutants such as personal care products, platicizers and flame retardants in sludge [J]. Anal Bio Anal Chem, 2009, 395(6): [12],,, [J]., 2014, 39(6): Zhao ZH, Zhu H, Liu M, et al. Determination on 18 phthalic acid esters (PAEs) in dairy by ulta performance liquid chromatography-tandem quadrupole mass spectrometry(uplc-ms/ms) [J]. Food Sci Technol, 2014, 39(6): [13] GB/T [S] GB/T Determination of phthalate esters in foods [S] [14] Cao XL. Phthalate esters in food: sources, occurrence, and analytical methods [J]. Compr Rev In Food Sci Food Saf, 2010, 9(1): [15],,. - [J]., 2015, 24(2): Liu MH, Chen ZT, Chen X. Determination of multi pesticide residues in EELS by GC-MS coupled with solid phase extraction [J]. Fujian Anal Testing, 2015, 24(2): 作者简介 ( 责任编辑 : 姚菲 ) 杜娟, 硕士, 中级工程师, 主要研究方向为食品安全 dujuanwenling@163.com

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