摘要
酞酸酯类化合物(Phthalic acid esters,简称PAEs)是塑料制品中不可缺少的一种改性添加剂。过去人们一直认为PAEs的毒性低,因而毫无限制地生产,但近年来的研究结果表明,尽管它们在环境中的残留量不大,急性毒性不明显,但具有致突变、致癌和致畸性,并可混合在食物、空气和其它物质中,通过消化、呼吸器官和皮肤进入人体,已对人体健康构成了潜在危害,故PAEs被称为“第二个全球性PCBs污染物”。
本学位论文致力于动物内脏,蔬菜以及塑料橡胶中十几种PAEs残留分析的方法研究,针对不同的样品体系,建立了以不同溶剂为提取剂的超声提取、Florisil硅土净化预分离、GC-EI/MS定性定量分析的方法,同时对PAEs的GC-MS/MS分析作了初步的探讨。全部内容分为以下五章:
第一章简要综述了目前国内外PAEs环境激素的研究内容。阐述了PAEs在大气、水体、泥土和生物体内的污染状况,并综述了PAEs残留的分析方法研究进展,同时讨论了该课题的研究意义,并对该课题的后续研究进行了展望。
第二章开展了动物内脏中14种PAEs残留的GC-EI/MS分析方法研究。初步解析了PAEs的EI/MS谱图;优化了样品的前处理条件;讨论了分析空白值的控制问题;准确分析了猪肝、鸭肝、鸡肝、牛肝以及猪心、鸭心中14种PAEs的含量,证实了PAEs环境环境激素在动物内脏中已经有了一定程度的蓄积。
第三章利用GC-EI/MS技术对16种PAEs化合物的同时分析进行了系统性的研究,建立了正己烷超声提取,Florisil硅土柱层析净化,正己烷/乙酸乙酯(3/2,v/v)洗脱的前处理方法。以苯甲酸苄基酯(BB)为内标物,采用内标法的定量方法对萝卜、茄子、马铃薯、卷心菜、冬瓜五种常见蔬菜中PAEs残留进行了分析。为掌握和有效的控制蔬菜等农产品的PAEs污染提供了依据。
第四章开展了塑料橡胶中13种常见PAEs增塑剂的GC-EI/MS的分析方法研究。采用外表法的定量方式,从方法检测限、准确度、精密度和线性范围四个指标考察了分析方法的可靠性。此外,本章特别对含有多种同分异构体的DINP的定量分析进行了初步的研究。
第五章对PAEs的GC-MS/MS分析方法进行了初步的研究探讨。以9种PAEs为研究对象,对MS/MS各分析参数,如目标物保留时间段、扫描时间、母离子的选择、目标物激发存储水平、碰撞诱导解离电压、共振或非共振MS/MS解离方式等进行了探讨和优选,最终建立了PAEs的GC-MS/MS分析方法。此外,还从响应信号和信噪比两个方面比较了离子存储技术(SIS)和MS/MS两种技术的优缺点。
Phthalic acid esters (PAEs ) are widely used as plasticizers all over the world. In the past year, people had thougt that they were less toxic, but recently, more and more investigations have shown that PAEs are Environmental Incretion. Usually, they combine with the food, the air and other things, coming into body through digestion, respiration or skin and leading to the instability of internal secretions. PAEs are toxic and harmful to hunman, so they are regarded as "The second global PCBs Pollutants" now.
This dissertation focused on the studies of different analytical methods for PAEs in different samples, such as animal innards, vegetables, plastics rubber and so on. The method was as following: extracted with different solvent against different samples, separated by Florisil diatomite, then analyzed by GC-EI/MS SIM. Furthermore, the analytical methods of PAEs by GC-MS/MS was discussed in this thesis preliminarily.
The first chapter, simply introduced the study of PAEs Environmental Incretion in China and abroad, which including the Pollution level of PAEs in different areas and the analytical method of PAEs. Finally, the plan of this dissertation as well as the outlook of the subject was also interpreted.
The second chapter, GC-EI/MS was applied to the determine of 14 PAEs simultaneously in animal innards. Firstly, the structures of PAEs fragments and their EI/MS rupture mechanisms were parsed. Then, the different parameters such as the extractant, the eluent and proportion of eluent were optimized during the pretreatment process., at the same time ,the problem of analytical blank was dissussed. Finally, PAEs were analyzed in six animal innards, such as pork liver, duck liver, chicken liver, beef liver and so on, confirming that PAEs have been accumulated in animal innards
The third chapter, an analytical method was developed for the simultaneous determination of 16 PAEs in vegetables by GC-EI/MS. PAEs were extracted with hexane in an ultrasonic bath and cleaned up on a Florisil column, then were determined by GC-EI/MS with Benzyl benzoate ( BB ) as internal standard. At last, the radish, brinjaul, potato, cabbage and wax gourd were analyzed, providing a effective measure for the control of PAEs pollution in vegetables.
The four chapter, developing a GC-EI/MS method for simultaneous determination of 13 PAEs in plastics rubber with external standard method in quantitative. The recoveries, limit of detection, precision and linear range were investigated to pledge the reliability. Furthermore, the quantitative problem of DINP with the isomers was dissussed especially
The fiver chapter, the analytical methods of PAEs by GC-MS/MS was discussed preliminarily in this thesis. Take 9 PAEs for example, several parameters for MS/MS such as scan time, parent ion, excitation storage level, CID voltage, the model of resonant and nonresonant and so on were optimized. Finally, the analytical method of 9 PAEs with GC-MS/MS was established. Furthermore, the MS/MS and SIS were compared in Sensitivity and S/N.
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