Microsoft Word 杜珍妮-二校 4627.doc

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1 6 11 Vol. 6 No Journal of Food Safety and Quality Nov., 2015 PVC 1, 杜珍妮 2, 苗宏健 2, 李敬光 2, 吴永宁 (1., ; 2.,, ) 2* 摘要 : 目的 PVC 方法 PVC (DIBP) (DBP) (2- ) (DEHP) (DEHA) 3% 10% 20% 50% 95%, PVC 结果 ; Fick, PVC, 结论关键词 : ; ; ; Research on the migration regularity and the modeling building of plasticizers in food contact material PVC DU Zhen-Ni 1, 2, MIA Hong-Jian 2, LI Jing-Guang 2, WU Yong-Ning 2* (1. College of Food Science and Engineering, Wuhan Polytechnic University, Wuhan , China; 2. Key Laboratory of Food Safety Risk Assessment, Ministry of Health, China National Center for Food Safety Risk Assessment, Beijing , China) ABSTRACT: bjective To study the migration rule of plasticizers from food contact material PVC under different food stimulants. Methods The content of plasticizer dilsobutyl phthalate (DIBP), dibutyl phthalate (DBP), di 2 ethyl hexyl phthalate (DEHP), and dioctyl adipate (DEHA) from PVC were detected by gas chromatography-mass spectrometry coupled with the isotope internal standard dilution. Migration behavior of plasticizer DIBP, DBP, DEHP, and DEHA intofood stimulants of 3% acetic acid and 10%, 20%, 50%, 95% ethanol was studied at 25 and 40. Results The food stimulants and temperature were proved to have effects on the migration of plasticizers. The mathematical models of four plasticizers migration which based by Fick s 2nd law was established and the models important parameters were also achieved. Conclusion The established models can effectively provide the food safety assessment. KEY WRDS: plasticizer; food contact material; food stimulants; migration model 基金项目 : ( , ) Fund: Supported by the National Natural Science Foundation of China ( , ) * 通讯作者 :,, wuyongning@cfsa.net.cn *Corresponding author: WU Yong-Ning, Researcher, China National Center of Food Safety Risk Assessment. wuyongning@cfsa.net.cn

2 引言 (PVC), PVC, PVC, (DIBP) (DBP) (2- ) (DEHP) (DEHA), PVC [1,2], GB 9685 [3] No 10/2011 [4] PVC [5-7],,,, No 10/2011 [4], PVC,,, Fick [6], PVC 2 材料与方法 2.1 材料试验材料 PVC ( 10-3 cm, DIBP DBP DEHA DEHP 2.30 % 3.04 % 3.04 % 4.75 %, ); 仪器与试剂 DSQ ( ); ( ); ( Scientific Industries ); ( - ); ( 74 mm, 100 ml, ) (CDN Isotopes INC., 100 μg/ml, ): DIBP DBP DEHP; DEHA (CDN Isotopes INC., 100 μg/ml, ); D 4 -DIBP D 4 -DBP D 4 -DEHP D 4 -DEHA(CDN Isotopes INC., 99.8 %); (TEDIA, Spectro grade, 99.5 %); (J.T.Baker, rganic Residue, 99.8 %); (J.T.Baker, Spectro grade, 99.5 %); 2.2 方法标准曲线 DIBP DBP DEHP DEHA, 10 μg/ml D 4 - D 4 -,, D 4 - D μg/ml, μg/ml 仪器条件 : DB-5 ms UI (30 m 0.25 mm 0.25 μm);, %,, 1.0 ml/min; 260 ; min; 20 /min 220, 1 min; 5 /min 280, 10 min; 20 /min 300, 1 min : ; 1 μl; 280 : (EI); 70 ev; 260 ; 6 min; (SIM), 1 表 1 塑化剂的定性及定量离子 Table 1 Qualitative and quantitative ions of plasticizer D 4 -DIBP 153 DIBP 149,223,104, D 4 -DBP 153 DBP 149,223,205, D 4 -DEHP 153 DEHP 149,167,279, D 4 -DEHA 133 DEHA 129,112,147,70 129

3 11, : PVC 迁移实验, 3% ( ) 10% 20% ( ) 50% 95% ( ), ( : cm 2, : 95 ml) [8] 10 cm 10 cm PVC,, PVC,,,, min 60 min 2 h 4 h 6 h 1 d 3 d 7 d 10 d 样品前处理 1 ml 10 ml, (10 μg/ml, )50 μl, 3% 10% 20%, 1 ml, 2 min, 3000 r/min 5 min, GC-MS ; 50% 95%,,, 20%(V:V) [9], DBP DIBP DEHP DEHA 迁移模型建立, ( ) PVC, ( 1) [6] C C P p = Dp (1) 2 t x 1, C P (mg/kg) t(s) x, D P (cm/s), PVC, -, 1, 2 2 m Ft, A ρ α 1+ α = cp,0 PdP ( + α) 2α 1 1 exp : 2 qn Dt 2 2 P 2 n= 11+ α + α q n dp P, F P P, P P (2) 1 V c F F, ρf VF α = = (3) K V c ρ V K PF, Cp, ρp = (4) C ρ F, tan q n = αq n (5), m F,t /A(mg/cm) P F t(s), ; A(cm 2 ), c P,0 (ng/g=μg/kg) P ; ρ P (g/cm) ρ F (g/cm) P F ; d P (cm) P, V P (cm 3 ) V F (cm 3 ) ; D P P ; K P,F, ( 4); q n 5 : (1), (2) P F, (3) 3 结果与讨论 3.1 食品模拟溶液对迁移的影响, 40, 10 d 1, DIBP DBP DEHP DEHA,,, [7],,, 20%,,, F

4 Fig. 1 Migration of four plasticizers into different stimulate solutions at 40 DEHP DEHA, 50% 95% [9],,,,, [6] 3.2 温度对迁移的影响, (25, 40, ), 2,,,, 25,, PVC,,,, PVC, PVC, [10,11], Arrhenius,,, [6] 3.3 其他因素对迁移的影响, (Log P) (, ) 2,

5 11, : PVC Fig. 2 Migration of four plasticizers into ethanol with different densities at 25 and 40 表 2 四种塑化剂在 25 40, 50 % 95 % 乙醇中的迁移率 Table 2 Migration rate of four plasticizers into 50 %, 95 % ethanol at 25 and 40 Log P (%) 25 50% 25 95% 40 50% 40 95% DIBP DBP DHEP DHEA

6 4632 6,, [12,13], ; DIBP DBP DEHP, Log P DEHP DBP DIBP,, DEHP DBP DIBP;,, DEHP DBP DIBP Fick,,,,, DEHP DBP DIBP,, DEHP DEHA 3% 10% 20%,,, 3.4 模型中的重要参数及模型评价 PVC, D, K Matlab (2), (6),, PVC, RSME(%) [6] : (6) N 5 2 : 3,,,, 3% DIBP, D ; K ,, DIBP, D K RSME 0.001%~5.109%,,, DBP 40 20% ( 3), 4,, PVC DBP 表 3 不同食品模拟溶液中的扩散系数分配系数及相对偏差 Table 3 Diffusion coefficients, K P/F and RSME values for different foodstuffs ( ) D(cm 2 /s) α RMSE(%) K P/F 25 3% DIBP DBP % DIBP DBP % DIBP DBP % DIBP DBP DEHP DEHA % DIBP

7 11, : PVC 4633 ( ) D(cm 2 /s) α RMSE(%) K P/F DBP DEHP DEHA % DIBP 续表 3 DBP % DIBP DBP % DIBP DBP % DIBP DBP DEHP DEHA % DIBP DBP 4.41 * DEHP DEHA 图 3 DBP 向 % 乙醇的迁移模型 Fig. 3 DBP migration model into 20 % ethanol at 40 表 4 DBP 在 % 乙醇下的预测值与实测值 Table 4 DBP s predicted value and measured value into 20 % ethanol at h 5.2 h 7.8 h 48 h 96 h 120 h 144 h 216 h (μg/dm 2 ) (μg/dm 2 )

4634 6 4 结论 PVC 3% 10% 20% 50% 95%, 25 40 PVC : PVC ; PVC : Fick PVC,,, 参考文献 [1] Wittassek M, Koch HM, Angerer J, et al. Assessing exposure to phthalates the human biomonitoring approach [J].

Phthalates and di-(2-ethylhexyl) adipate (DEHA) intake by German infants based on the results of a duplicate diet study and biomonitoring data (INES 2) [J]. Food Chem Toxicol, 2013, 53: 272 280.

8 结论 PVC 3% 10% 20% 50% 95%, PVC : PVC ; PVC : Fick PVC,,, 参考文献 [1] Wittassek M, Koch HM, Angerer J, et al. Assessing exposure to phthalates the human biomonitoring approach [J]. Mol Nutr Food Res, 2011, 55(1): [2] Fromme H, Gruber L, Schuster R, et al. Phthalates and di-(2-ethylhexyl) adipate (DEHA) intake by German infants based on the results of a duplicate diet study and biomonitoring data (INES 2) [J]. Food Chem Toxicol, 2013, 53: [3] GB [S]. GB Hygienic standards for uses of additives in food containers and packaging materials [S]. [4] fficial Journal of the European Union. Commission Regulation (EU) No 10/2011 of 14 January on plastic materials and articles intended to come into contact with food [S]. [5] Xu Q, Yin XY, Wang M, et al. Analysis of phthalate migration from plastic containers to packages cooking oil and mineral water [J]. J Agric Food Chem, 2010, 58(10): [6] Silva AS, Cruz Freire JM, Franze R, et al. Migration and diffusion of Diphenylbutadiene from packages into foods [J]. J Agric Food Chem, 2009, 57(21): [7] Coltro L, Pitta BJ, da Costa PA, et al. Migration of conventional and new plasticizers from PVC films into food stimulants: A comparative study [J]. Food Control, 2014, 44(1): [8] GB/T [S]. GB/T Materials and articles in contact with foodstuffs Plastics substances subject to limitation Guide to test methods for the specific migration of substances from plastics to foods and food stimulants and the determination of substances in plastics and the selection of conditions of exposure to food stimulants [S]. [9],,,. [J]., 2014, 43(3): Miao HJ, Fang CR, Lu J, et al. Determination phthalates in Chinese spirits [J]. J Hyg Res, 2014, 43(3): [10],. PE UV [J]., 2009, 25(7): Huang XL, Wang ZW. Migration behavior of UV Ink photo-initiators from paper through PE coating into food stimulants [J]. Polym Mater Sci Eng, 2009, 25(7): [11],,,. Tenax [J]., 2014, 35(9): Wang N, Hu CY, Cheng J, et al. Migration of phthalate acid esters of paper-made food packing into Tenax and milk powder [J]. Sci Technol Food Ind, 2014, 35(9): [12],,,. [J]., 2007, 35(4): Hu LJ, Chen LQ, Zhang XY, et al. Application and development of frost resisting plasticizer [J]. Plastics Sci Technol, 2007, 35(4): [13],,,. [J]., 2015, 36(11): Li CC, Lin W, Huang CX, et al. Migration of EDCs in plastic packaging under microwave heating [J]. Packag Eng, 2015, 36(11): 作者简介 ( 责任编辑 : 白洪健 ) 杜珍妮, 硕士研究生, 主要研究方向为食品科学 @qq.com 吴永宁, 研究员, 主要研究方向为食品安全 wuyongning@cfsa.net.cn

Microsoft Word 王颖-二校

Microsoft Word 王颖-二校 7 10 Vol. 7 No. 10 2016 10 Journal of Food Safety and Quality Oct., 2016 王 * 颖, 刘海韵, 张桂芳, 王志昱, 张晓瑜, 孙兆鹏 (, 264003) 摘要 : 目的方法 GB/T 21911-2008, : (1:1, V:V),, 结果,, (2- ) (DEHP)70% (DBP)60% (DIBP)45% (DINP)20%,