本文選題：母乳 + 有機(jī)氯農(nóng)藥代謝物　； 參考：《復(fù)旦大學(xué)》2012年碩士論文

【摘要】：持久性O(shè)CPs及其代謝物通過(guò)食物鏈的傳遞在人體脂肪組織、血清和母乳中富集,嚴(yán)重危害人體健康。在以往母乳中OCPs的監(jiān)測(cè)中,都是將有機(jī)氯原形和一些簡(jiǎn)單的初級(jí)代謝物列入研究對(duì)象,為了進(jìn)一步完善持久性O(shè)CPs組分的檢測(cè),使得OCPs對(duì)機(jī)體負(fù)荷與暴露評(píng)估研究更為全面、充分,本文首次將檢測(cè)對(duì)象擴(kuò)大為OCPs及初級(jí)、次級(jí)代謝物7大類27個(gè)組分。為了進(jìn)一步提高檢測(cè)的靈敏度、準(zhǔn)確度、穩(wěn)定可靠性和實(shí)驗(yàn)室易操作性,本文從樣品前處理(包括提取、凈化手段和同位素稀釋技術(shù))和儀器分析(包括色譜分離以及質(zhì)譜類型和方法條件)等方面進(jìn)行了深入研究。同時(shí)利用已建立的方法對(duì)上海地區(qū)2010-2012年采集的100份母乳樣品進(jìn)行了測(cè)定,一方面驗(yàn)證的該方法的實(shí)用性,另一方面將測(cè)定結(jié)果與上海市2002～2010年的污染水平,與歐美日韓等發(fā)達(dá)國(guó)家、亞非等發(fā)展中國(guó)家的污染水平進(jìn)行了比較,分析上海地區(qū)居民母乳中持久性O(shè)CPs蓄積水平、變化趨勢(shì),以及在世界所處的水平。 本論文研究?jī)?nèi)容主要摘要如下： 第一章介紹了OCPs和代謝物產(chǎn)生的過(guò)程以及造成的危害�？偨Y(jié)和歸納了目前國(guó)內(nèi)外關(guān)于母乳及乳制品中OCPs和代謝物分析方法的研究進(jìn)展,最后闡述了論文研究的意義和內(nèi)容。 第二章詳細(xì)闡述了母乳中OCPs和代謝物檢測(cè)方法建立的過(guò)程。對(duì)于母乳中痕量檢測(cè)的要求,為了進(jìn)一步提高檢測(cè)的靈敏度和準(zhǔn)確度,前處理采用加速溶劑萃取(ASE)提取,凝膠色譜(GPC)和固相萃取(SPE)聯(lián)合凈化的方法,即使樣品濃縮250倍,本底仍較低,干擾小。選用待測(cè)物的同位素作為內(nèi)標(biāo),一些新的代謝物采用保留時(shí)間接近,化學(xué)性質(zhì)相似的同位素內(nèi)標(biāo),減少了樣品前處理和進(jìn)樣過(guò)程中帶來(lái)的損失。儀器分析方法通過(guò)實(shí)驗(yàn)考察比較GC-MS和GC-MS/MS兩種技術(shù),最后確定氣相色譜-串聯(lián)質(zhì)譜(GC-MS/MS)法,該方法抗基質(zhì)干擾能力強(qiáng),增強(qiáng)了定性和定量準(zhǔn)確性,提高了檢測(cè)的靈敏度和準(zhǔn)確度。方法學(xué)驗(yàn)證結(jié)果表明：在0.5～100ng/mL范圍內(nèi)線性良好,相關(guān)系數(shù)R2大于0.998。方法靈敏度很高,27個(gè)目標(biāo)分析物的最小檢出限0.066～1.7ng/kg。與文獻(xiàn)報(bào)道的方法相比,靈敏度提高了100倍。方法的準(zhǔn)確度和精密度良好,在較低的加標(biāo)水平下,取得良好的回收率。牛奶加標(biāo)水平0.016μg/kg,回收率為60.2%～123.7%,相對(duì)標(biāo)準(zhǔn)偏差小于13.5%；牛奶加標(biāo)水平0.08μg/kg,回收率為70.1%～119.8%,相對(duì)標(biāo)準(zhǔn)偏差小于14.4%。方法學(xué)驗(yàn)證結(jié)果表明：所建立的分析方法靈敏度高、干擾小和選擇性好,符合母乳樣品中持久性O(shè)CPs痕量檢測(cè)的要求,是母乳等含脂肪類生物樣品較為理想的分析方法。 第三章對(duì)100份母乳樣品的檢測(cè)結(jié)果進(jìn)行分析和討論。檢測(cè)結(jié)果顯示隨著檢測(cè)方法靈敏度提高,檢出率了很大提高,除了δ-HCH檢出率為54%外,其余組分的檢出率在76%以上。在OCPs污染物中,滴滴涕類和六六六類仍是主要的污染成分,含量達(dá)到251583pg/g lipid wt、62404pg/g lipid wt(平均值)。與2002-2010年母乳監(jiān)測(cè)結(jié)果相比有了顯著程度的下降,與歐美發(fā)達(dá)國(guó)家的差距也在逐步縮小。污染物檢出率較高,部分代謝物如六氯苯、DDE含量仍較高,對(duì)健康風(fēng)險(xiǎn)不可忽視。因此,應(yīng)加強(qiáng)持久性O(shè)CPs污染狀況的持續(xù)監(jiān)測(cè)。本次監(jiān)測(cè)監(jiān)測(cè)中,一些新的高毒性有機(jī)氯農(nóng)藥代謝物如DDMU、DDM、DDOH、DBP、硫丹內(nèi)酯、硫丹醚的檢出率很高,也應(yīng)考慮將這些代謝物納入持久性O(shè)CPs監(jiān)測(cè)范疇,以便能更準(zhǔn)確地得到OCPs在生物體中變化的趨勢(shì),暴露的內(nèi)劑量水平,使得OCPs對(duì)機(jī)體負(fù)荷與暴露評(píng)估研究更為全面、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.

【學(xué)位授予單位】：復(fù)旦大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2012
【分類號(hào)】：O657.63;R114

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本文編號(hào)：1825754