【作者】 房丽萍；

【导师】 杨桂朋； 牛增元；

【作者基本信息】 中国海洋大学 ， 环境科学， 2004， 硕士

【摘要】 环境激素是环境中存在的一类化学物质，它可以改变人类和动物的内分泌系统，导致生殖、发育和行为异常。邻苯二甲酸酯类化合物就是其中一类重要的环境激素，它主要用作增塑剂。近年来，随着塑料制品的大量生产和使用，邻苯二甲酸酯不断进入环境，已成为全球性的最普遍的一类污染物。 本论文选定被广泛关注的11种邻苯二甲酸酯类环境激素(DMP、DEP、DPrP、DBP、DAP、DHP、BBP、DEHP、DnOP、DiNP、DiDP)作为研究对象，使用气相色谱仪、气-质联用仪、高效液相色谱仪三种色谱分析仪器，经过大量的条件实验，系统地研究并建立了GC-FID、GC-MSD、HPLC-DAD三种同时测定11种邻苯二甲酸酯类环境激素的分析方法，并且对三种方法的线性范围、线性相关性以及最低检出限做了比较，很好地满足了邻苯二甲酸酯类环境激素的分析检测在不同情况下的需要。 邻苯二甲酸酯类化合物被广泛地应用在工业领域的各个方面，国际上已经开始重视邻苯二甲酸酯作为一种内分泌干扰素的危害性，对在一些产品中的用量作出了限制，但没有具体的分析测定方法，本论文结合国际法规选择了与人们生活密切相关的涂料和纺织品来研究其中邻苯二甲酸酯类环境激素的测定方法，研究内容如下： (1)通过对提取溶剂、提取方式、提取时间的选择实验以及固相萃取的一系列条件实验，首次建立了纺织品中测定邻苯二甲酸酯类环境激素的前处理方法，并对分析方法作了准确度、精密度验证。结果表明，邻苯二甲酸酯类各化合物的回收率在80.30％-98.00％之间，相对标准偏差RSD在0.59％-2.56％之间，说明本方法准确可靠。 (2)采用PTFE膜过滤前处理法，首次建立了涂料中苯系物和邻苯二甲酸酯类环境激素的同时测定方法，并对分析方法作了准确度、精密度以及实验室间验证。结果表明，邻苯二甲酸酯类各化合物的回收率在96.01％-102.02％，相对标准偏差RSD在0.92％-2.46％之间，说明本方法简便、快速、灵敏、精密度好。 邻苯二甲酸酯类环境激素与人体会有经常的接触，研究它们在人造体液(如汗液、唾液)中的迁移规律具有重大的现实意义。本论文选择三种常用有代表性邻苯二甲酸醋类环境激素分析方法及迁移规律研究的邻苯二甲酸醋类化合物(DEP、DBP、DnOP)，以纺织品为基质研究它们在酸性汗液中的溶出量随时间、温度、振动频率的不同而变化的规律，具体研究内容如下: (l)邻苯二甲酸醋类化合物的水溶性较低，需要对汗液进行浓缩富集，本论文通过一系列的条件实验，建立了固相萃取的最佳条件。依次用2 mL甲醇、2 mL蒸馏水活化固相萃取柱，汗液流速为5 mUmin:洗脱剂为丙酮，洗脱体积为2 mL，洗脱速率为1 mUmin。洗脱液经无水硫酸钠脱水后，进气相色谱分析。 (2)分别改变振动时间、温度、频率来研究随着这些影响因素的变化，DEP、DBP、DnOP在汗液中溶出量的变化。通过实验发现:DEP的溶出量远远大于DBP和DnOP，DEP、DBP、DnOP的溶出量随着时间的增长溶出量逐渐增大，开始时随时间增大明显，后期增长缓慢;溶出量随温度升高而增大，温度低时变化不明显，温度高时明显;振动频率对溶出量的影响不如时间、温度的影响大，总趋势是随着频率的升高溶出量增大。更多还原

【Abstract】 Environmental hormone is a class of chemical compounds in environment. It may affect human and animals on their normal endocrines, leading to reproductive, developmental and behavioral disorder. Phthalic acid esters (PAEs) are an important group of environmental hormones. Their main application is as plasticizers in the manufacture of plastics. In recent years, large amounts of plastics have caused a wide distribution of PAEs into environment. PAEs have become one of the most prevalent contaminants in the world.Eleven phthalic acid esters (DMP, DEP, DPrP, DBP, DAP, DHP, BBP, DEHP, DnOP, DiNP, DiDP) have been studied by gas chromatography, gas chromatography-mass spectrometry, high performance liquid chromatography technology in this thesis. The effect of operating condition of gas chromatography such as flow rate, temperature of injection, detector and column and high performance liquid chromatography such as column, mobile phase on the response and separation of PAEs are investigated and acquire optimum operating condition. The ranges of linearity, corrections of linearity and the detection limits for the three simultaneous determinations of eleven PAEs also have been compared.Phthalic acid esters are widely used in the many fields of industry. So many countries including China have come to pay attention to them and make up the codes for limiting the content in some products such as textile. By combining international codes, the thesis selects coating and textile that have close relative with people as objections. The research results are as follows:1. The thesis has established the textile’s preparation method by a series of experimentations such as extraction solvent, extraction time, solid-phase extraction. The average recoveries of eleven phthalates are from 80.30% to 98.00%, and the relative standard deviations (RSDs) from 0.59% to 2.56%, the results show that this method is accurate and credible.2. The thesis set up the simultaneous determination of benzene, toluene, xylenes and phthalates in coatings. Most of film-forming matters, filling pigments and all kinds of particulate additives are removed by inert PTFE filter membrane. The average recoveries of benzene, toluene, (p, m)-xylenes, o-xylene are from 97.21% to 103.10% and the RSDs are from 0.12% to 0.95%. And the average recoveries of Phthalic acid ester are from 96.01% to 102.02% and the RSDs are from 0.92% to 2.46%. The results show that this method is simple, fast and accurate with high reproducibility and high sensitivity.The thesis has studied the migration rules of DEP, DBP, DnOP from the textile matrix to acidic sweat. The research results are as follows:1. Phthalic acid esters are slightly soluble in water, which make it necessary to pretreatment before determination. The optimum condition and procedure of solid phase extraction (SPE) are established as following: active cartridge using 2mL methanol and 2mL distilled water respectively before pretreatment, control sample loading rate at 5mL/min, eluting rate at 1.0mL/min, select 2mL ethyl acetate as eluting solvent, dehydrate the elute by anhydrous sodium sulfate.2. By changing the factors such as librating of time, temperature, frequency, the migration rules of DEP, DBP, DnOP are discussed in the thesis. The sequence of the dipped amount is DEP>DBP>DnOP. And the dipped amounts of DEP, DBP, DnOP are rising as time and temperature increasing. Liberating frequency is less effective than time and temperature, but the general trend is rising.更多还原