塑料中内分泌干扰物的含量检测与来源分析(原)

Chemical Analysis of Endocrine Disrupting Compounds of Food packaging Plastic Film

Chongxing Huang*, Wen Lin, Cuicui Li, Dongjie Xue

（College of Light Industry & Food Engineering, Guangxi University, Nanning, 530004, China）

摘要：Contamination of foodstuffs by environmental pollutants receives much attention. Until recently, food packaging as a source of xenobiotics, especially those with

endocrine disrupting properties, has received little awareness despite its ubiquitous use. This study presents the research on the analysis of endocrine disrupting compounds, DEA, DBP, BBP, DEHA,DEHP, BHT, BHA,BP and MBP of 4 common used composite packaging films in food-contacted, which belonged plasticizer, Antioxidant，UV absorber. In the chemical analysis, composite films were extracted by acetone under ultrasonic condition, and analysis by gas chromatography/mass spectrometry. The sources of the 9 endocrine disrupting

compounds were analysis and its content were compared with the related laws and regulations.

研究结果表明，四种塑料中除了DEHA没有检出外，其他组分都有检测到. 并且,这些组分在塑料基材和油墨中都有分布，说明它们都是常用的添加剂，在树脂成型和油墨印刷中都发挥作用。DBP在未印刷的四种塑料薄膜样品中的含量是15.67-20.73 ug/g，在印刷后的四种塑料薄膜样品中的含量是25.60-38.90 ug/g。BBP在未印刷的四种塑料薄膜样品中的含量是14.26-20.83 ug/g，而在印刷后的四种塑料薄膜样品中的含量是17.72-29.97 ug/g。DEHP未印刷的四种塑料薄膜样品中的含量是165.91-226.38 ug/g, 在印刷后的四种塑料薄膜样品中的含量是298.36-369.88 ug/g. BHT在未印刷的四种塑料薄膜样品中的含量是6.26-7.98 ug/g，在印刷后的四种塑料薄膜样品中的含量是10.11-10.26 ug/g。BHA在未印刷的四种塑料薄膜样品中的含量是157.93-213.27 ug/g，在印刷后的四种塑料薄膜样品中的含量是201.97-326.56. BP在未印刷的四种塑料薄膜样品中的含量是0.78-1.17 ug/g，在印刷后的四种塑料薄膜样品中的含量是2.58-2.81 ug/g. MBP在未印刷的四种塑料薄膜样品中的含量是4.12-5.82 ug/g，在印刷后的四种塑料薄膜样品中的含量是6.56-8.86 ug/g。

在所有的8种未印刷和印刷后的样品中，除了DEHA在所有的样品中没有被检出以外，Larger amount of EDCs were found in printed products than unprinted products.将检测结果与欧盟标准EU 10-2011中相关规定进行对比发现，塑料样品中相关物质的含量都在规定范围内。

关键词：内分泌干扰物；复合包装薄膜，气相色谱-质谱联用

INTRODUCTION

环境内分泌干扰物（Endocrine Disrupting Chemicals, EDCs）是一类广泛分布于环境和食物、包装、玩具等各类消费品中的可以对人体内激素含量产生影响的物质[1,2]，是一种外源性干扰人体内分泌系统的化学物质，它们通过逐步摄入、积累等途径，而不是直接作为有毒有害物质给生物体带来不利影响，像雌激素类物质那样对生物体产生作用，即使数量微少，也可能让生物体的内分泌系统失去平衡，出现各种异常现象。内分泌干扰物多为有机污染物及重金属物质。近年来随着经济社会的发展和工业化程度的提高，EDCs在自然界和人类社会中的分布范围、含量及暴露途径也随之变广、增多[3-5]。伴随着全球工业化的浪潮，EDCs在医药制造领域、添加剂加工领域（主要用于塑料、橡胶）、除草剂生产方面的使用十分普遍，它们会在产品的使用和废弃处理等过程中释放出来，对生态环境造成巨大的压力和危害。大多数EDCs都不易降解，不仅能够在食物链中循

环，又能够随着自然界的生态循环而在各个地区和国家游走，因此，内分泌干扰物是一种持续性的并且是区域性甚至全球性的威胁。

The packaging market is a highly important industrial sector, approximately equal in size

to the pharmaceutical industry. In 2007, global market value amounted to around US $530 billion, with food and beverage packaging constituting more than half of all packaging uses (food 41%, industry and transport 21%, other 17%, beverages 14%, pharmaceuticals 4%, and cosmetics 3%) (Pira International, in: Schönrock 2008). When broken down by packaging material, the most important consumer packaging (by market value) is made of plastic (38%, both rigid and flexible plastics), followed by paper and cardboard (30%), metal (19%), glass (8%), and others (5%) (Pira International, in: Rexam, 2008). Around 70% of overall consumer packaging consumption is used for food and beverage packaging (Pira International, in:

World Packaging Organization, 2008).Food as a major xenobiotics and heavy metal exposure route to humans is studied intensively. Typical food contaminants, like pesticides, dioxins, PCBs, PBDEs, methylmercury, lead, arsenic, etc. are well characterized in food, with high public and regulatory awareness, as a recent debate on pesticides in food shows, spurred by an NGOs report (Schafer and Kegley, 2002). In contrast, the role of food and beverage packaging as an additional source of contaminants has received much less attention, even though food packaging contributes significantly to human xenobiotic exposure (Grob et al., 2006). This may now be changing. For example, a fierce public debate has unfolded during

the past 5 years over the potential safety of bisphenol A (BPA), a plastic monomer that is one

of the highest production–volume chemicals worldwide. BPA is extensively used in many different types of food packaging and a known endocrine disruptor (vom Saal et al., 2007). In fact, many intentionally-used substances in food packaging have been identified as endocrine disruptors in biological systems. Therefore, it is important to consider food packaging as an important route of endocrine disrupting compounds (EDCs) exposure to humans by leaching from the packaging into the food and the environment by waste disposal.

在与人们生活息息相关的食品药品包装方面，内分泌干扰物带来的威胁也与日俱增。目前，用于食品包装的聚合物主要有聚乙烯、聚丙烯、聚酰胺、聚酯、聚氯乙烯等高分子材料[6]。这些塑料材料多以复合薄膜的形式在包装中使用。为了改善塑料包装材料的加工性能和其制品的使用性能，往往在塑料的生产过程中添加一些化学添加剂，比如光稳定剂、抗氧化剂、增塑剂、热稳定剂、抗静电剂、紫外线吸收剂、阻燃剂、防霉剂等。在印刷过程中使用的油墨，其组分中的油墨残留溶剂；复合包装材料用粘合剂；存在于油墨组分中的铅、镉、汞、铬等重金属和苯胺、稠环化合物是包装材料中油墨危害的三个来源[7]。除此之外，油墨中增塑剂、光引发剂、抗氧化剂等添加剂向食品的迁移而产生的食品安全问题近年来出现比较频繁，越来越多的研究人员开始关注这个方面。若干研究表明：油墨中的光引发剂和增塑剂较易通过包装材料向食品迁移，故近年来UV 油墨中的光引发剂的迁移已经引起人们注意[8]。

在塑料包装材料和食品接触过程中，一旦条件适宜，聚合物包装材料中的小分子添加剂、游离单体、大分子降解产物等会向食品中迁移[9,10]，进而进入人体循环系统。这些物质在包装材料和食品接触的过程中迁移进入食品，一方面会对被包装食品造成污染，另一方面会对降低包装材料物理性能，降低包装对内容物的保护功能而导致食品营养成分的流失、风味价值降低甚至变质，使消费者的健康受到威胁[11]。另外聚合物在加工过程中受到如高温、辐射、高压等处理，在食用过程中受到如蒸煮、微波、煎炸等的影响，