母乳中持久性有机氯农药及代谢物残留的分析方法研究及应用

发布时间：2018-04-30 18:51

本文选题：母乳 + 有机氯农药代谢物　；参考：《复旦大学》2012年硕士论文

【摘要】：持久性OCPs及其代谢物通过食物链的传递在人体脂肪组织、血清和母乳中富集,严重危害人体健康。在以往母乳中OCPs的监测中,都是将有机氯原形和一些简单的初级代谢物列入研究对象,为了进一步完善持久性OCPs组分的检测,使得OCPs对机体负荷与暴露评估研究更为全面、充分,本文首次将检测对象扩大为OCPs及初级、次级代谢物7大类27个组分。为了进一步提高检测的灵敏度、准确度、稳定可靠性和实验室易操作性,本文从样品前处理(包括提取、净化手段和同位素稀释技术)和仪器分析(包括色谱分离以及质谱类型和方法条件)等方面进行了深入研究。同时利用已建立的方法对上海地区2010-2012年采集的100份母乳样品进行了测定,一方面验证的该方法的实用性,另一方面将测定结果与上海市2002～2010年的污染水平,与欧美日韩等发达国家、亚非等发展中国家的污染水平进行了比较,分析上海地区居民母乳中持久性OCPs蓄积水平、变化趋势,以及在世界所处的水平。本论文研究内容主要摘要如下：第一章介绍了OCPs和代谢物产生的过程以及造成的危害。总结和归纳了目前国内外关于母乳及乳制品中OCPs和代谢物分析方法的研究进展,最后阐述了论文研究的意义和内容。第二章详细阐述了母乳中OCPs和代谢物检测方法建立的过程。对于母乳中痕量检测的要求,为了进一步提高检测的灵敏度和准确度,前处理采用加速溶剂萃取(ASE)提取,凝胶色谱(GPC)和固相萃取(SPE)联合净化的方法,即使样品浓缩250倍,本底仍较低,干扰小。选用待测物的同位素作为内标,一些新的代谢物采用保留时间接近,化学性质相似的同位素内标,减少了样品前处理和进样过程中带来的损失。仪器分析方法通过实验考察比较GC-MS和GC-MS/MS两种技术,最后确定气相色谱-串联质谱(GC-MS/MS)法,该方法抗基质干扰能力强,增强了定性和定量准确性,提高了检测的灵敏度和准确度。方法学验证结果表明：在0.5～100ng/mL范围内线性良好,相关系数R2大于0.998。方法灵敏度很高,27个目标分析物的最小检出限0.066～1.7ng/kg。与文献报道的方法相比,灵敏度提高了100倍。方法的准确度和精密度良好,在较低的加标水平下,取得良好的回收率。牛奶加标水平0.016μg/kg,回收率为60.2%～123.7%,相对标准偏差小于13.5%；牛奶加标水平0.08μg/kg,回收率为70.1%～119.8%,相对标准偏差小于14.4%。方法学验证结果表明：所建立的分析方法灵敏度高、干扰小和选择性好,符合母乳样品中持久性OCPs痕量检测的要求,是母乳等含脂肪类生物样品较为理想的分析方法。第三章对100份母乳样品的检测结果进行分析和讨论。检测结果显示随着检测方法灵敏度提高,检出率了很大提高,除了δ-HCH检出率为54%外,其余组分的检出率在76%以上。在OCPs污染物中,滴滴涕类和六六六类仍是主要的污染成分,含量达到251583pg/g lipid wt、62404pg/g lipid wt(平均值)。与2002-2010年母乳监测结果相比有了显著程度的下降,与欧美发达国家的差距也在逐步缩小。污染物检出率较高,部分代谢物如六氯苯、DDE含量仍较高,对健康风险不可忽视。因此,应加强持久性OCPs污染状况的持续监测。本次监测监测中,一些新的高毒性有机氯农药代谢物如DDMU、DDM、DDOH、DBP、硫丹内酯、硫丹醚的检出率很高,也应考虑将这些代谢物纳入持久性OCPs监测范畴,以便能更准确地得到OCPs在生物体中变化的趋势,暴露的内剂量水平,使得OCPs对机体负荷与暴露评估研究更为全面、充分。
[Abstract]:Persistent OCPs and its metabolites are enriched in human body fat tissue, serum and breast milk through the transmission of food chain, which seriously harm human health. In the monitoring of OCPs in human breast milk, the organic chlorine origin and some simple primary metabolites were included in the study. In order to improve the detection of persistent OCPs components, the OCPs pair The study of body load and exposure assessment is more comprehensive and full. This article is the first time to expand the detection object to OCPs and primary and secondary metabolites in 7 categories and 27 components. In order to further improve the sensitivity, accuracy, stability and reliability of the test, the sample pretreatment (including extraction, purification and isotope dilution techniques) An in-depth study was carried out with the instrumental analysis (including chromatographic separation, mass spectrometry and method conditions). At the same time, 100 samples of breast milk samples collected in 2010-2012 years in Shanghai area were measured. On the one hand, the practicability of the method was verified. On the other hand, the results were determined with the city of Shanghai for 2002~2010 years. The pollution level is compared with the pollution levels of the developed countries such as Europe, America, Japan, Japan and other developing countries, such as Asia, Africa and other developing countries. It analyses the persistent OCPs accumulation level, the trend of change and the level in the world of Shanghai residents' breast-feeding.
The main contents of this paper are as follows:
The first chapter introduces the process and harm of OCPs and metabolites, summarizes and summarizes the research progress on the analysis methods of OCPs and metabolites in breast milk and dairy products at home and abroad, and finally expounds the significance and content of the research.
The second chapter elaborated on the process of establishing OCPs and metabolite detection methods in breast milk. For trace detection in breast milk, in order to further improve the sensitivity and accuracy of detection, preprocessing using accelerated solvent extraction (ASE) extraction, gel chromatography (GPC) and solid phase extraction (SPE) combined purification method, even if the sample is concentrated 250 times, this The base remains low and the interference is small. Select the isotopes of the objects to be measured as internal standard, some new metabolites with close time and similar chemical properties, reduce the loss in the process of sample pretreatment and sampling. The instrumental analysis method compares the two techniques of GC-MS and GC-MS/MS by experimental investigation, and finally determines the gas chromatography. The method of tandem mass spectrometry (GC-MS/MS), which has strong anti matrix interference ability, enhanced the qualitative and quantitative accuracy and improved the sensitivity and accuracy of the detection. The results of validation of the methodology show that the sensitivity is good in the range of 0.5 to 100ng/mL, the correlation coefficient R2 is more sensitive than the 0.998. method, and the minimum detection limit of the 27 target analytes is 0.066 to 1. The sensitivity of.7ng/kg. is 100 times higher than that reported in the literature. The accuracy and precision of the method are good. The recovery rate is good under the lower standard level. The milk addition level is 0.016 mu g/kg, the recovery rate is 60.2% ~ 123.7%, the relative standard deviation is less than 13.5%, the milk addition level is 0.08 g/kg, and the recovery rate is 70.1% to 119.8%, The results of relative standard deviation less than 14.4%. methodology show that the proposed method has high sensitivity, small interference and good selectivity, which is in line with the requirements of trace detection of persistent OCPs in breast milk samples, and is an ideal analysis method for breast milk and other fatty biological samples.
In the third chapter, the results of 100 samples of breast milk were analyzed and discussed. The detection results showed that the detection rate was greatly improved as the sensitivity of the detection method increased. In addition to the delta -HCH detection rate of 54%, the detection rate of the other components was more than 76%. In the OCPs pollutants, DDT and 666 types were still the main pollution components. 251583pg/g lipid WT, 62404pg/g lipid WT (average). Compared with the results of breast milk monitoring in 2002-2010 years, there is a significant decline, and the gap with developed countries in Europe and the United States is also gradually narrowing. The detection rate of pollutants is higher, some metabolites such as six chlorobenzene, DDE content is still higher, the health risk can not be ignored. Therefore, the persistence of OCPs pollution should be strengthened. Therefore, the persistent OCPs pollution should be strengthened. Therefore, the persistent OCPs pollution should be strengthened. The detection rate of some new high toxic organochlorine pesticides, such as DDMU, DDM, DDOH, DBP, endosulfan and endosulfan, is very high in this monitoring and monitoring. It is also necessary to consider the inclusion of these metabolites into the persistent OCPs monitoring category so that the tendency of OCPs to change in the organism can be more accurately obtained, and the exposure dose of water is more accurate. This makes OCPs more comprehensive and adequate for the study of body load and exposure assessment.

【学位授予单位】：复旦大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：O657.63;R114

【参考文献】