Microsoft Word 李俊_二校出4131

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1 7 10 Vol. 7 No Journal of Food Safety and Quality Oct., * 李俊, 郭晓关, 杜楠 (, ( ), ) 摘要 : 目的 - - (gel permeation chromatography-gas chromatography-mass spectrometry, GPC-GC-MS) (phthalate acid esters, PAEs) 方法, GPC-GC-MS PAEs 结果 0.10~10.0 mg/l, PAEs (r ), 0.7~2.8 μg/l, 2.3~9.2 μg/l; mg/ml 3, PAEs 80.4%~95.6%, 1.5%~6.5% 结论,, PAEs 关键词 : ; ; ; - Rapid determination of phthalate acid esters in liquor by on-line gel permeation chromatography-gas chromatography-mass spectrometry LI Jun, GUO Xiao-Guan, DU Nan * (Guizhou Provincial Supervision and Testing Center for Agricultural Product Quality, Supervision and Safety Risk Evaluation Laboratory for Agricultural Product Quality, Ministry of Agriculture (Guiyang), Guiyang , China) ABSTRACT: Objective To establish a method for determination of phthalate acid esters (PAEs) in liquor by on-line gel permeation chromatography-gas chromatography-mass spectrometry (GPC-GC-MS). Methods Without pretreatment, the liquor sample was analyzed by GPC-GC-MS for its content of PAEs after being mixed. Results There were good linear relationships between the peak areas of PAEs and their corresponding concentration which ranged from 0.10 mg/l to 10.0 mg/l with correlation coefficients not less than The limits of detection of method were 0.7~2.8 μg/l, the limits of quantification were 2.3~9.2 μg/l, and the average recoveries of PAEs ranged from 80.4% to 95.6% at 3 different spiked levels with the relative standard deviations were between 1.5% and 6.5%. Conclusion This method is simple, quick, and has low risks of plasticizer contamination, high automation, accuracy, precision and sensitivity, which is suitable for the rapid analysis of PAEs in liquor. KEY WORDS: liquor; phthalate acid esters; gel permeation chromatography; gas chromatography-mass spectrometry * 通讯作者 :,, E-mall: dsn5168@163.com *Corresponding author: DU Nan, Senior Engineer, Guizhou Provincial Supervision and Testing Center for Agricultural Product Quality, Supervision and Safety Risk Evaluation Laboratory for Agricultural Product Quality, Ministry of Agriculture (Guiyang), Guiyang , China. E-mall: dsn5168@163.com

2 引言 (phthalate acid esters, PAEs),,, [1,2] PAEs,, [3-8], PAEs,,, PAEs, PAEs, [9-11] 20 90, , -, [9-12], PAEs, [13-15] - [16-19] [20,21] - [22,23] [9] ,,, -,,,,, - - (gel permeation chromatography-gas chromatographymass spectrometry, GPC-GC-MS) 2 材料与方法 2.1 仪器与试剂 QP ( ) (, ); ( ); 16 : (DMP) (DEP) (BBE) (DIBP) (DBP) (2- ) (DMEP) ( ) (BMPP) (2- ) (DEEP) (DPP) (DHXP) (BBP) (DHP) (2- ) (DBEP) (DCHP) (2- ) (DEHP) (DNOP), 1000 mg/l, Dr. Ehrenstorfer 2.2 实验方法样品处理,, 仪器条件 (1) : Shodex CLNpak EV-200 (2.1 mm 150 mm); : - (3:7, V:V); : 0.1 ml/min; : 40 ; : 20 μl (2) : (5 m 0.53 mm), : Rtx-5 MS (5 m 0.25 mm, 0.25 μm), : Rtx-5 MS(25 m 0.25 mm, 0.25 μm); (programmed temperature vaporizerptv) ; ; : 80 5 min, 100 /min min; 0~5 min 50, 5~8 min 0, 8~10 min 50;, 100 kps; : 60 1 min, 20 /min min, 5 /min min.; : 280 (3) : 280 ; : (electron impact ion source, EI); : 70 ev; : (selected ion monitoring, SIM); 6 min 结果与讨论 3.1 样品处理方法选择,,,,,,,, [8,9],,,,,

3 10, : Table 1 表 1 16 种邻苯二甲酸酯的保留时间和定性定量离子 The retention time, qualitative and quantitative ions of 16 kinds of PAEs (min) (m/z) (m/z) 1 DMP DEP BBE DIBP DBP (2- ) DMEP ( ) BMPP (2- ) DEEP DPP DHXP BBP DHP (2- ) DBEP DCHP (2- ) DEHP DNOP , 98, 2,,, GPC-GC-MS, 20 μl GPC,,, 3.2 在线凝胶色谱净化,, PAEs, - (3:7, V:V); 0.1 ml/min; 40 ; 20 μl GPC,, 3.8 min, 5.2 min GPC 0~3.5 min, GPC 3.5~5.6 min 3.3 气相色谱测定 [9] 16 PAEs GC-MS, 16 PAEs - 1, 16 PAEs, 3.4 质谱测定 280,, 70 ev, 10 mg/l PAEs 50~300, ±2.5%, [24], PAEs 3.5 标准工作曲线的绘制 50% mg/l PAEs,,,, 0.10~10.00 mg/l, 16 PAEs, r 回收率和精密度实验 50%,

4 4134 7, mg/l 3,, 6, 3 PAEs 80.4%~95.6 %, (relative standard deviation, RSD) 1.5%~6.5 %,,, R S/N =3 (limit of detection, LOD), R S/N =10 (limit of quantitation, LOQ), 2, 0.7~2.8 μg/l, 2.3~9.2 μg/l 1 16 PAEs - Fig. 1 Total ion current chromatogram in GC-MS of 16 kinds of PAEs 1. DMP; 2. DEP; 3. BBE; 4. DIBP; 5. DBP; 6. DMEP; 7. BMPP; 8. DEEP; 9. DPP; 10. DHXP; 11. BBP; 12. DHP; 13. DBEP; 14. DCHP; 15. DEHP; 16. DNOP Table 2 表 2 方法的相关系数检出限定量限和回收率 (n=6) Correlation coefficients, LODs, LOQs and recoveries of the method (n=6) PAEs r 2 LOD(μg/L) LOQ(μg/L) Recovery (%) RSD(%) DMP DEP BBE DIBP DBP DMEP BMPP DEEP DPP DHXP BBP DHP DBEP DCHP DEHP DNOP

5 10, : 样品测定 3 PAEs, 3, PAEs, RSD 8.56%, PAEs 表 3 白酒样品测定结果 (n=7) Table 3 Determination results of liquor samples (n=7) (μg/l) RSD(%) PAEs DMP DEP BBE DIBP DBP DMEP BMPP DEEP DPP DHXP BBP DHP DBEP DCHP DEHP DNOP : - 4 结论 GC-MS PAEs mg/l 3, PAEs 80.4%~95.6%, RSD 1.5%~6.5%; 0.7~2.8 μg/l, 2.3~9.2 μg/l,, PAEs 参考文献 [1],,,. [J]., 2003, 13(1): Hu XY, Zhang KR, Sun JH, et al. Environmental comamination by phthalates in China [J]. Chin J Health Lab Technol, 2003, 13(1): [2],. [J]., 2004, 26(19): Liu HJ, Shu WQ. Toxicological effect and risks of phthalate acid esters on the health of population [J]. Acta Acad Med Mil Tert, 2004, 26(19): [3]. [J]., 2013, (4): Liu MH. Hazards and preventive analysis of plasticizers [J]. J Green Sci Technol, 2013, (4): [4],,,. [J]., 2010, 27(2): Zhao YH, Wang XY, Ling XT, et al. Advances in researches on metabolic mechanism and toxicity of phthalate esters [J]. J Environ Health, 2010, 27(2): [5]. [J]., 2012, 37(2): Guo YM. Toxicity and related restricted laws and regulations for phthalate esters [J]. Guangzhou Chem, 2012, 37(2): [6],,,. [J]., 2014, 24(4): Wang H, Peng J, Zhu KZ, et al. Harmfulness of white plasticizer and its countermeasure [J]. Chin J Health Lab Technol, 2014, 24(4): [7],,. [J]., 2003, 25(5): Lin XT, Wang XY, Ren R. Environmental endocrine disruptors--a study of phthalate esters [J]. Environ Pollut Control, 2003, 25(5): [8],,. [J]., 2008, (1): Chen HT, Wei DY, Guo ZY. Progress in the analysis of phthalic acid esters [J]. Plast Addit, 2008, (1): [9],,. [J]., 2012, 222(12): Li J, Guo XG, Du N. Determination of phthalate ester residues in white spirit by gas chromatography-quadrupole mass spectrometry [J]. Liq-Mak Sci Technol, 2012, 222(12): [10] Chales AS, Dennis RD. The environmental fate of phtalate esters-a literature review [J]. Chemoshere, 1997, 35(4): [11] Bonni M, Errani E, Zerbinati G, et al. Extraction and gas chromatographic evaluation of plasticizers content in food packaging films [J]. Microchem J, 2008, 90(1): [12] Commission directive(ec). No.2007/19 Laying down the list of simulants to be used for testing migration of constituents[s]. [13],,,. - [J]., 2014, 30(1): Shen F, Su XY, Li R, et al. Determination of phthalate esters in water by solid-phase extraction and gas chromatography [J]. Environ Monit China, 2014, 30(1): [14] Holadova K, Prokupkova G, Hajslova J, et al. Headspace solid-phase microextraction of phthalic acid esters from vegetable oil employing solvent based matrix modification [J]. Anal Chim Acta, 2007, 582(1): [15] Zhu HL, Cui SM, Wang WP, et al. Determination of phthalate esters in

4136 7 wine using dispersive liquid-liquid microextraction and gas chromatography [J]. Anal Lett, 2014, 47(11): 1874 1887. [16],,,. - [J]., 2014, 35(9): 127 130. Wang S, Wang K, Zhu HP, et al.

Analytical method for the identification and assay of 12 phthalates in cosmetic products: application of the ISO 12787 international standard Cosmetics-Analytical methods-validation criteria for

6 wine using dispersive liquid-liquid microextraction and gas chromatography [J]. Anal Lett, 2014, 47(11): [16],,,. - [J]., 2014, 35(9): Wang S, Wang K, Zhu HP, et al. Study of phthalates detection in oil by gas chromatography-mass spectrometry [J]. Food Res Dev, 2014, 35(9): [17] Gimeno P, Maggio AF, Bousquet C, et al. Analytical method for the identification and assay of 12 phthalates in cosmetic products: application of the ISO international standard Cosmetics-Analytical methods-validation criteria for analytical results using chromatographic techniques [J]. J Chromatogr A, 2012, 1253: [18],,,. - [J]., 2014, 5(9): Li SJ, Chen QY, Mi JB, et al. Uncertainty evaluation of the determination of bis-butyl ester in win by gas chromatography-mss spectroscopy [J]. J Food Saf Qual, 2014, 5(9): [19] Ma TT, Teng Y, Peter C, et al. A new procedure combing GC-MS with accelerated solvent extraction for the analysis of phthalic acid ester in contaminated soils [J]. Front Environ Sci Eng China, 2013, 7(1): [20],,,. [J]., 2009, 28(6): Wang ML, Chen HT, Zhang HN, et al. Determination of 5 phthalates in meat by high performance liquid chromatography [J].Chin J Anal Lab, 2009, 28(6): [21],,,. 8 [J]., 2014, 35(18): Tang L, Bo DG, Xia JF, et al. Determination of eight phthalic acid esters in freshwater shellfish by high performance liquid chromatography [J]. Sci Technol Food Ind, 2014, 35(18): [22] Prasad B, Suresh S. Biodegradation of phthalate esters by variovorax sp [J]. Apcbee Procedia, 2012, 1(3): [23],,,. - A 15 [J]., 2014, 5(8): Jing P, Zhang JD, Zhu WB, et al. Determination of bisphenol A(BPA) and 15 phthalate esters(paes) by high performance liquid chromatographytandem mass spectrometry in beverage, milk and milk powder [J]. J Food Saf Qual, 2014, 5(8): [24] Commission decision of 12 august 2002 implementing council directive 96/23/EC concerning the performance of analytical methods and the interpretation of results [J]. Off J Eur Comm, 2002, L221: 作者简介 ( 责任编辑 : 刘丹 ) 李俊, 硕士, 高级实验师, 主要研究方向为食品安全及仪器分析 JunL82@163.com 杜楠, 高级工程师, 主要研究方向为食品安全及仪器分析 dsn5168@163.com

Microsoft Word 徐幸-new_校对稿_

Microsoft Word 徐幸-new_校对稿_ 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)

Microsoft Word 李 俊_二校出4131

Microsoft Word 李俊_二校出4131