Zhang Tiantian, Ye Xiwen, Luo Xin, Niu Zengyuan, Wang Huiyong, Ma Qiang
Technology Center of Qingdao Customs, Qingdao, 266000, China.
Chinese Academy of Inspection and Quarantine, Beijing, 100176, China.
Anal Bioanal Chem. 2023 Sep;415(22):5463-5473. doi: 10.1007/s00216-023-04819-z. Epub 2023 Jul 10.
The purpose of this study was to offer a quick and efficient method to screen for multiple restricted additives in polymer materials. A solvent-free pyrolysis gas chromatography-mass spectrometry method was developed to simultaneously screen 33 restricted substances, comprising 7 phthalates, 15 bromine flame retardants, 4 phosphorus flame retardants, 4 ultraviolet stabilizers, and 3 bisphenols. The pyrolysis technique and temperatures affecting additive desorption were studied. Under optimized conditions, the instrument sensitivity was confirmed using in-house reference materials at concentrations of 100 mg/kg and 300 mg/kg. The linear range was between 100 and 1000 mg/kg in 26 compounds, and in the other compounds it was between 300 and 1000 mg/kg. In this study, in-house reference materials, certified reference materials, and proficiency testing samples were used for method verification. The relative standard deviation of this method was less than 15%, and recoveries ranged from 75.9 to 107.1% for most of the compounds, with a few exceeding 120%. Furthermore, the screening method was verified with 20 plastic products used in daily life and 170 recycled plastic particle samples from imports. The experimental results showed that phthalates were the main additives in plastic products, and among 170 recycled plastic particle samples, 14 samples were found to contain restricted additives. The main additives in recycled plastics were bis(2-ethylhexyl) phthalate, di-iso-nonyl phthalate, hexabromocyclododecane, and 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether at concentrations between 374 and 34785 mg/kg, except for some results that exceeded the maximum measured value of the instrument. Compared with traditional methods, an important advantage is that this method simultaneously tests for 33 additives without sample pretreatment, covering a variety of additives limited by laws and regulations, and therefore can provide more comprehensive and thorough inspections.
本研究的目的是提供一种快速有效的方法,用于筛选聚合物材料中的多种受限添加剂。开发了一种无溶剂热解气相色谱 - 质谱法,用于同时筛选33种受限物质,包括7种邻苯二甲酸盐、15种溴系阻燃剂、4种磷系阻燃剂、4种紫外线稳定剂和3种双酚。研究了热解技术以及影响添加剂解吸的温度。在优化条件下,使用浓度为100 mg/kg和300 mg/kg的内部参考物质确认了仪器灵敏度。26种化合物的线性范围为100至1000 mg/kg,其他化合物的线性范围为300至1000 mg/kg。在本研究中,使用内部参考物质、有证参考物质和能力验证样品进行方法验证。该方法的相对标准偏差小于15%,大多数化合物的回收率在75.9%至107.1%之间,少数超过120%。此外,用20种日常生活中使用的塑料制品和170个进口回收塑料颗粒样品对该筛选方法进行了验证。实验结果表明,邻苯二甲酸盐是塑料制品中的主要添加剂,在170个回收塑料颗粒样品中,有14个样品被发现含有受限添加剂。回收塑料中的主要添加剂是邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二异壬酯、六溴环十二烷和2,2',3,3',4,4',5,5',6,6'-十溴二苯醚,浓度在374至34785 mg/kg之间,但有些结果超过了仪器的最大测量值。与传统方法相比,该方法的一个重要优点是无需样品预处理即可同时检测33种添加剂,涵盖了各种法律法规限制的添加剂,因此可以提供更全面、彻底的检测。