【摘要】：內(nèi)分泌干擾污染物(EDCs)是能夠模擬/模擬生物體對(duì)內(nèi)源性激素的分子效應(yīng),干擾或阻止激素正常合成、釋放、結(jié)合、代謝等過(guò)程的一些天然和人工合成化合物。EDCs可能導(dǎo)致動(dòng)物生殖系統(tǒng)異常、性別紊亂、免疫力及生育力降低等。EDCs廣泛存在于世界各地的多種環(huán)境介質(zhì)中。然而,關(guān)于EDCs的生物富集及其機(jī)理的系統(tǒng)研究還很有限。為此,本研究選取10種典型EDCs包括對(duì)羥基苯甲酸甲酯(MP)、對(duì)羥基苯甲酸乙酯(EP)、對(duì)羥基苯甲酸丙酯(PP)、對(duì)羥基苯甲酸丁酯(BP),鄰苯基苯酚(PHP)、三氯生(TCS)、雙酚A(BPA)三氯卡班(TCC)及其脫氯產(chǎn)物二環(huán)己基碳二亞胺(DCC)和均二苯脲(NCC)。系統(tǒng)研究珠江水系野生淡水水生生物中這些EDCs的富集、生物食物鏈放大潛力以及相應(yīng)的影響因素,主要結(jié)論如下:(1)采用旋渦振蕩-超聲波輔助萃取結(jié)合凝膠滲透色譜除去大分子有機(jī)物干擾,再經(jīng)硅膠柱層析進(jìn)一步凈化,建立生物樣品中微/痕量?jī)?nèi)分泌干擾污染物的UHPLC-MS/MS分析方法,該方法的定量限為0.1~9.7 ng/g dw,回收率為65.2%~118.0%。(2)除NCC以外,EDCs廣泛分布于珠江水系淡水野生生物中。EDCs的分布存在一定的種間差異,TCC只在甲殼綱中檢出,且占EDCs總濃度的56%,檢出率為100%,次為PHP和MP;而硬骨魚(yú)綱中則以BPA為最,檢出率為96.67%,次為T(mén)CS和MP。另外,EDCs在生物中的分布與食性呈現(xiàn)出一定的關(guān)系,肉食性魚(yú)類(lèi)脊肉中MP的濃度明顯高于其他魚(yú)類(lèi),濃度范圍為402.52 ng/g lw;肉食性魚(yú)類(lèi)脊肉中TCS和BPA的濃度明顯低于其他魚(yú)類(lèi),范圍分別為ND和21.90ng/glw。(3)EDCs在珠江水系野生淡水魚(yú)類(lèi)中的富集水平存在明顯的組織差異。MP、TCS和BPA在魚(yú)類(lèi)組織器官中的濃度和生物富集因子(logBAF)基本上表現(xiàn)為肝臟腩脊肉,說(shuō)明肝臟的富集能力最強(qiáng),腩次之,脊肉最弱。(4)EDCs在珠江水系野生淡水魚(yú)類(lèi)中的分布與其生活環(huán)境緊密相關(guān),總的來(lái)看,珠江廣州河段魚(yú)中EDCs濃度較高,尤其是MP、TCS和BPA;EDCs的生物富集表現(xiàn)出一定的季節(jié)特征,如MP、TCS和BPA在廣東魴脊肉中濃度表現(xiàn)為雨季高于旱季。生物的個(gè)體特征對(duì)其中EDCs的分布存在明顯影響,如隨生物體重的增加,脊肉中的MP的濃度呈上升趨勢(shì),而TCS的濃度呈下降趨勢(shì)。生物性別也對(duì)其中EDCs的富集存在明顯影響。如MP在雌性福壽魚(yú)脊肉中的濃度高于雄性,TCS在雌性銀鯽魚(yú)和廣東魴脊肉中的濃度亦高于雄性,BPA則在在雌性赤眼鱒和福壽魚(yú)脊肉中的濃度也高于雄性。(5)EDCs有一定的生物放大潛力和子代傳遞效應(yīng)。如TCS的營(yíng)養(yǎng)級(jí)放大因子(TMF)為1.62,可能沿生態(tài)食物鏈放大,BPA的TMF為0.92,而MP的TMF為0.33,表明可能隨著食物鏈產(chǎn)生生物稀釋作用。MP、TCS和BPA均可能發(fā)生母子傳遞效應(yīng)。
[Abstract]:Endocrine disrupting pollutant (EDCs) can simulate / simulate the molecular effects of endogenous hormones, interfere with or prevent the normal synthesis, release and binding of hormones. Some natural and synthetic compounds such as metabolism. EDCs may lead to abnormal reproductive system, sex disorder, decreased immunity and fertility, and so on. EDCs are widely found in many environmental media all over the world. However, systematic studies on the bioconcentration and mechanism of EDCs are limited. To that end, In this study, 10 typical EDCs including methyl p-hydroxybenzoate (MP), ethyl p-hydroxybenzoate (EP), propyl p-hydroxybenzoate (PP), p-hydroxybenzoate (BP), p-hydroxybenzoate (PHP), (TCS), bisphenol A (BPA), triclosan (TCC) (TCS),) and their dechlorination were selected. Product dicyclohexyl carbodiimide (DCC) and (NCC). The enrichment of these EDCs in wild freshwater aquatic organisms in the Pearl River system, the amplification potential of biological food chain and the corresponding influencing factors were systematically studied. The main conclusions are as follows: (1) using vortex oscillation-ultrasonic assisted extraction combined with gel permeation chromatography to remove the interference of macromolecular organic matter and further purifying by silica gel column chromatography. A UHPLC-MS/MS method for the determination of micro- / trace endocrine disrupting pollutants in biological samples was established. The quantitative limit of this method is 0.1 ~ 9.7 ng/g dw, recovery rate of 65.2% ~ 118.0. (2) there are some interspecific differences in the distribution of ng/g dw, except NCC in freshwater wildlife of Pearl River system. The detectable rate of the total concentration of EDCs is 56. The detectable rate is 100. The second is PHP and MP;, while BPA is the most. The detection rate is 96.67, the second is TCS and MP., and the second is TCS and MP.. In addition, there was a certain relationship between the distribution of MP and their feeding habits. The concentration of MP in the spinal flesh of carnivorous fish was significantly higher than that of other fishes, and the concentration of TCS and BPA in the spinal flesh of carnivorous fish was significantly lower than that of other fishes in the range of 402.52 ng/g lw;. The range was ND and 21.90 ng / glw. (3) there were significant tissue differences in the enrichment levels of EDCs in wild freshwater fishes in the Pearl River system. The concentrations of EDCs and BPA in fish tissues and organs and bioenrichment factor (logBAF) were basically shown as liver brisket. The results showed that the liver had the strongest enrichment ability, followed by the brisket, and the spinal meat was the weakest. (4) the distribution of EDCs in the wild freshwater fish in the Pearl River system was closely related to its living environment. In general, the concentration of EDCs in the fish in the Guangzhou reach of the Pearl River was higher than that in the fish in the Guangzhou reach of the Pearl River. In particular, the bioconcentration of MP,TCS and BPA;EDCs showed seasonal characteristics, such as the concentration of MP,TCS and BPA in the ridge of Bream bream was higher in rainy season than in dry season. The distribution of EDCs was significantly influenced by the individual characteristics of the organism. For example, with the increase of biological weight, the concentration of MP in spinal meat increased, while the concentration of TCS decreased. Sex also had a significant effect on the enrichment of EDCs. If the concentration of MP in female Fushou fish is higher than that of male in female Carassius auratus and bream, the concentration of MP in female red trout and Fushou fish is also higher than that in male. (5) there is a certain percentage of EDCs in female red trout and Fushou fish. Magnification potential and progeny transfer effect. For example, the nutritional factor (TMF) of TCS is 1.62. the TMF of TCS may be 0.92 along the ecological food chain, while the TMF of MP is 0.33, which indicates that the mother-child transmission effect may occur with the biofilution of food chain.
【學(xué)位授予單位】：中國(guó)科學(xué)院大學(xué)(中國(guó)科學(xué)院廣州地球化學(xué)研究所)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：X52;X171.5

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