研究报告

PET/PE复合膜中初级芳香胺及2种塑料添加剂的迁移研究及安全评估

  • 罗任杰 ,
  • 林勤保 ,
  • 颜建伟 ,
  • 马俊杰 ,
  • 李忠
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  • 1(暨南大学 包装工程研究所,广东 珠海,519070)
    2(华东交通大学 土木建筑学院,江西 南昌,330052)
    3(拱北海关技术中心,广东 珠海,519020)
硕士研究生(林勤保研究员和颜建伟教授为共同通讯作者,E-mail:tlinqb@jnu.edu.cn;tyanjianwei@jnu.edu.cn)

收稿日期: 2021-01-12

  修回日期: 2021-03-05

  网络出版日期: 2021-08-23

基金资助

国家重点研发计划项目(2018YFC1603206;2018YFC1603204);国家自然科学基金优青培育项目(20202ZDB01001);珠海进出口公共技术服务平台产学研协同创新计划(IETP202001006)

Migration and safety assessment of primary aromatic amines and two plastic additives from PET/PE composite films

  • LUO Renjie ,
  • LIN Qinbao ,
  • YAN Jianwei ,
  • MA Junjie ,
  • LI Zhong
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  • 1(Packaging Engineering Institute,Jinan University,Zhuhai 519070,China)
    2(School of Civil Engineering and Architecture,East China Jiaotong University,Nanchang 330052,China)
    3(Gongbei Customs Technology Center,Zhuhai 519020,China)

Received date: 2021-01-12

  Revised date: 2021-03-05

  Online published: 2021-08-23

摘要

首先对聚对苯二甲酸乙二醇酯/聚乙烯复合膜(polyethylene terephthalate/polyethylene composite film,PET/PE)及聚对苯二甲酸乙二醇酯/铝/聚乙烯复合膜(PET/AL/PE)的乙酸乙酯超声提取液进行筛查,确定高响应峰初级芳香胺(primary aromatic amines,PAAs)、4,4′-二氨基二苯硫醚、爽滑剂芥酸酰胺(erucamide,EAD)和抗氧剂2246作为目标检测物。结合筛查结果建立同时测定25种PAAs、EAD及抗氧剂2246的高效液相色谱-串联质谱方法:配制质量体积分数4%乙酸溶液、10%和95%的乙醇溶液作为食品模拟液,按照标准要求分别进行40 ℃/10 d以及70 ℃/2 h的迁移试验。浸泡液经过滤后直接进样,分别以H-ESI+和H-ESI-模式进行定量分析。3种食品模拟物中的25种PAAs及2种塑料添加剂标准品在其对应浓度范围线性良好,相关系数均大于0.997 3,各个物质在3个浓度水平的加标回收率范围为76.9%~108.2%,相对标准偏差为4%~12.5%;在40 ℃/10 d条件下2种复合膜中PAAs的迁移量为3~298 μg/L,在70 ℃/2 h下为3~118 μg/L;EAD在2种迁移条件下的迁移量为30~880 μg/L,抗氧剂2246迁移量为9~210 μg/L。迁移结果表明:40 ℃/10 d条件下迁移出的PAAs种类及迁移量均高出70 ℃/2 h条件下的迁移量;在较低使用温度(40 ℃)下,复合膜镀铝可以有效地减少芳香胺及添加物的迁出;pH值会对PAAs的迁移产生影响:PAAs更易于在中性和油性模拟物中迁出,在酸性模拟物中的迁移明显减弱。安全评估的结果为抗氧剂2246的迁移量低于国标和欧盟的限量,EAD的迁移量低于TTC法估算的安全阈值,而检出的芳香胺浓度均不能满足欧盟标准的要求,存在安全风险。

本文引用格式

罗任杰 , 林勤保 , 颜建伟 , 马俊杰 , 李忠 . PET/PE复合膜中初级芳香胺及2种塑料添加剂的迁移研究及安全评估[J]. 食品与发酵工业, 2021 , 47(15) : 120 -128 . DOI: 10.13995/j.cnki.11-1802/ts.026615

Abstract

Detection for PET/PE composite film was conducted by ultra high-performance liquid chromatography mass spectrometry (UPLC-MS/MS), and one primary aromatic amines (PAAs) Bis(4-aminophenyl) sulfide as well as two plastic additives erucamide (EAD) and antioxidant 2246 (AO2246) were detected. Then the migration of PET/PE and PET/AL/PE in composite films under 40 ℃/10 d and 70 ℃/2 h conditions immersed in three kinds of simulants (4% acetic acid, 10% and 95% ethanol) were carried out. The proposed method could simultaneously to determine 25 PAAs and EAD in ESI+ mode, and also to investigate AO2246 in ESI-mode. It was validated in terms of linearity, matrix effect error, detection and quantification limits, repeatability and intermediate precision. The quantitative method presented recoveries ranging from 82.7% to 119%, with a precision (RSD) lower than 12.5% for the 27 substances. Based on the experimental results, several conclusions were drawn as follows. Firstly, the species and amount of PAAs migrated at 40 ℃/10 d were higher than those at 70 ℃/2 h. And time was the main factor affecting PAAs’ migration and higher temperatures may lead to more PAAs released. Secondly, the migration of both PAAs could be effectively reduced by aluminum layer at a low temperature. Thirdly, the difference among the results in three kinds of simulants suggested that pH could also has an impact that acidic condition weakened PAAs’ migration. Last but not the least, the migration of EAD and AO2246 was lower than TTC safety threshold and national standard GB 9685 respectively. However, PAAs’ content could not meet the requirement of European Union standard, which indicates high safety risk.

参考文献

[1] 孙利, 陈志锋,储晓刚.浅析食品接触材料中的芳香胺问题[J].食品与机械,2006,22(6):121-126.
SUN L,CHEN Z F,CHU X G.Analysis of primary aromatic amines in food contact materials[J].Food & Machinery,2006,22(6):121-126.
[2] 白晨艳. 浅谈食品软包装中的初级芳香胺[J].粘接,2020,41(1):41-44.
BAI C Y.Primary aromatic amine in food flexible packaging[J].Adhesion,2020,41(1):41-44.
[3] (EU) 2020/1245.Amending and correcting Regulation (EU) No 10/2011 on plastic meterials and articles intended to come into contact with food[S].European Commission.2020.
[4] Commission Regulation (EU) No 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food[S].European Commission,2011.
[5] HUANG X J,QIU N N,YUAN D X,et al.Sensitive determination of strongly polar aromatic amines in water samples by stir bar sorptive extraction based on poly(vinylimidazole-divinylbenzene) monolithic material and liquid chromatographic analysis[J].Journal of Chromatography A,2009,1 216(20):4 354-4 360.
[6] 高杰, 张勋,杨璐,等.9类生态纺织品中24种禁用偶氮染料残留的测定[J].化学试剂,2017,39(2):165-171.
GAO J,ZHANG X,YANG L,et al.Determination of 24 banned azo colourants in 9 textiles[J].Chemical Reagents,2017,39(2):165-171.
[7] 韩玲. 食品接触塑料中初级芳香胺检测方法分析[J].食品安全导刊,2018(9):100.
HAN L.Analysis of detection methods for primary aromatic amines in food contact plastics[J].China Food Safety Magazine,2018(9):100.
[8] DEVREUX V,COMBET S,CLABAUX E,et al.From pigments to coloured napkins:Comparative analyses of primary aromatic amines in cold water extracts of printed tissues by LC-HRMS and LC-MS/MS[J].Food Additives & Contaminants:Part A,2020,37(11):1 985-2 010.
[9] MERKEL S,KAPPENSTEIN O,SANDER S,et al.Transfer of primary aromatic amines from coloured paper napkins into four different food matrices and into cold water extracts[J].Food Additives & Contaminants:Part A,2018,35(6):1 223-1 229.
[10] YAVUZ O,VALZACCHI S,HOEKSTRA E,et al.Determination of primary aromatic amines in cold water extract of coloured paper napkin samples by liquid chromatography-tandem mass spectrometry[J].Food Additives & Contaminants:Part A,2016,33(6):1 072-1 079.
[11] PEREZ M Â F,PADULA M,MOITINHO D,et al.Primary aromatic amines in kitchenware:Determination by liquid chromatography-tandem mass spectrometry[J].Journal of Chromatography A,2019,1602:217-227.
[12] 李全忠, 周明辉,刘莹峰,等.液相色谱-串联质谱法测定食品接触材料中28种初级芳香胺的迁移量[J].分析化学,2013,41(1):25-30.
LI Q Z,ZHOU M H,LIU Y F,et al.Determination of migration of 28 primary aromatic amines from food contact materials by liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2013,41(1):25-30.
[13] OUYANG X K,LUO Y Y,WANG Y G,et al.Validation a solid-phase extraction-HPLC method for determining the migration behaviour of five aromatic amines from packaging bags into seafood simulants[J].Food Additives & Contaminants:Part A,2014,31(9):1 598-1 604.
[14] MORETA C,TENA M T.Determination of plastic additives in packaging by liquid chromatography coupled to high resolution mass spectrometry[J].Journal of Chromatography A,2015,1414:77-87.
[15] SANCHIS Y,COSCOLLÁ C,YUSÁ V.Comprehensive analysis of photoinitiators and primary aromatic amines in food contact materials using liquid chromatography high-resolution mass spectrometry[J].Talanta,2019,191:109-118.[LinkOut]
[16] 陈志锋, 刘晓华,孙利.高效液相色谱法测定复合塑料食品包装中初级芳香胺的迁移量[J].包装工程,2010,31(3):48-51.
CHEN Z F,LIU X H,SUN L.Determination of the migration of primary aromatic amines from composite plastic food packaging by high performance liquid chromatography[J].Packaging Engineering,2010,31(3):48-51.
[17] 隋海霞, 刘兆平.我国食品接触材料安全性评估体系构建[J].中国食品卫生杂志,2018,30(6):551-557.
SUI H X,LIU Z P.Establishment of safety assessment system for food contact materials in China[J].Chinese Journal of Food Hygiene,2018,30(6):551-557.
[18] 王杰, 谭雄翠,陈东鹏,等.食品接触材料中多种添加剂高通量检测方法的研究[J].食品工业,2018,39(11):305-309.
WANG J,TAN X C,CHEN D P,et al.Study on high-throughput detection method of various additives in food contact materials[J].The Food Industry,2018,39(11):305-309.
[19] LV G,WANG L B,LIU J,et al.Method for determination of fatty acid amides in polyethylene packaging materials—Gas chromatography/mass spectrometry[J].Journal of Chromatography A,2009,1216(48):8 545-8 548.
[20] 王建玲, 肖晓峰,杨娟娟,等.高效液相色谱-串联质谱法同时检测食品接触材料中9种抗氧剂的特定总迁移量[J].分析试验室,2015,34(9):1 051-1 057.
WANG J L,XIAO X F,YANG J J,et al.Simultaneous determination of total specific migration limit of nine antioxidants in food simulants by high performance liquid chromatography-tandem mass speetrometry[J].Chinese Journal of Analysis Laboratory,2015,34(9):1 051-1 057.
[21] 杨璐, 周国桁,焦毅,等.高效液相色谱内标法检测塑料中芥酸酰胺[J].分析仪器,2019(2):66-69.
YANG L,ZHOU G H,JIAO Y,et al.Determination of erucamide in plastics by HPLC using internal standard method[J].Analytical Instrumentation,2019(2):66-69.
[22] 蒙芳玲, 胡长鹰,黎梓城,等.液相色谱串联质谱法测定铝塑复合膜中芥酸酰胺和油酸酰胺[J].食品与发酵工业,2020,46(20):208-213.
MENG F L,HU C Y,LI Z C,et al.Determination of erucamide and oleamide in aluminum-plastic compound film by liquid chromatography tandem mass spectrometry[J].Food and Fermentation Industries,2020,46(20):208-213.
[23] DOPICO-GARCÍA M S,LÓPEZ-VILARIÑÓ J M,GONZÁLEZ-RODRÍGUEZ M V.Antioxidant content of and migration from commercial polyethylene,polypropylene,and polyvinyl chloride packages[J].Journal of Agricultural and Food Chemistry,2007,55(8):3 225-3 231.
[24] 周建科, 张前莉,韩康,等.油炸食品中两种酚类抗氧剂的反相高效液相色谱法测定[J].食品研究与开发,2006,27(7):166-168.
ZHOU J K,ZHANG Q L,HAN K,et al.Determination of two phenolic antioxidants in fried foods by the reversed-phase HPLC[J].Food Research and Development,2006,27(7):166-168.[知网]
[25] 贾婧姝. 气相色谱法测定塑胶跑道面层中游离TDI含量[J].建筑科学,2017,33(7):28-32.
JIA J S.Detection of free TDI in synthetic material sports field by gas chromatography[J].Building Science,2017,33(7):28-32.
[26] CAMPANELLA G,GHAANI M,QUETTI G,et al.On the origin of primary aromatic amines in food packaging materials[J].Trends in Food Science & Technology,2015,46(1):137-143.
[27] 中华人民共和国国家质量监督检验检疫总局.SNT/2893—2011(2015).出口食品接触材料.高分子材料.食品模拟物中芳香族伯胺检测[S].北京:中国标准出版社,2011.
General Administration of Quality Supervision,Inspection and Quarantine of the People’s Republic of China.SNT/2893—2011 (2015).Export of food contact materials.Macromolecular materials.Detection of primary aromatic amines in food simulants[S].Beijing:China Standard Press,2011.
[28] 张力群, 任韧,金铨,等.液液萃取-气相色谱-质谱法测定涉水管材水浸液中17种邻苯二甲酸酯类化合物[J].中国卫生检验杂志,2016,26(24):3 504-3 507;3 511.
ZHANG L Q,REN R,JIN Q,et al.Determination of 17 phthalate esters in water soaking solution of plastic pipes for water supply by gas chromatography-mass spectrography[J].Chinese Journal of Health Laboratory Technology,2016,26(24):3 504-3 507;3 511.
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