本文選題：松花江　切入點(diǎn)：雌激素　出處：《哈爾濱工業(yè)大學(xué)》2014年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：雌激素和孕激素是重要的內(nèi)分泌干擾物，這類(lèi)物質(zhì)在環(huán)境中極其微量的存在都有可能對(duì)生態(tài)系統(tǒng)及人類(lèi)健康造成潛在危害。研究這類(lèi)物質(zhì)在松花江哈爾濱段的分布情況，能夠幫助全面了解松花江的水質(zhì)狀況，為相關(guān)研究和決策提供數(shù)據(jù)支持。 本文利用在線(xiàn)固相萃取技術(shù)，建立了水中雌激素和孕激素類(lèi)物質(zhì)的UPLC-MS/MS分析方法，該方法對(duì)各雌激素和孕激素的檢測(cè)限為0.1~1.0ng/L，滿(mǎn)足痕量分析的要求。 通過(guò)對(duì)松花江哈爾濱段的水體進(jìn)行采樣分析，發(fā)現(xiàn)該江段內(nèi)雌激素E1、E2、E3和EE2的濃度范圍分別為ND~25.5ng/L、 ND~9ng/L、 ND~19.5ng/L和ND~8.7ng/L，孕激素CPA、LNG的濃度范圍分別為ND~12.7ng/L、ND~3.4ng/L，孕激素GES在所有水樣中未檢出。雌激素和孕激素總濃度在該江段內(nèi)呈現(xiàn)江南高于江北，下游高于上游，冰雪消融期和豐水期高于枯水期的規(guī)律。在人類(lèi)活動(dòng)比較集中的采樣點(diǎn)以及河溝匯入口下游的采樣點(diǎn)，雌激素和孕激素的濃度有所增加。通過(guò)對(duì)比E1和E2的濃度之比，推測(cè)水中雌激素的存在與人類(lèi)的活動(dòng)有很大關(guān)系。 生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)表明，松花江哈爾濱段的水體中E1、E2、E3和LNG的存在具有一定的生態(tài)風(fēng)險(xiǎn)，需要采取相關(guān)措施。雌激素活性分析同樣表明，該江段內(nèi)大部分采樣點(diǎn)的EEQ值高于預(yù)測(cè)無(wú)影響濃度，需要采取相關(guān)措施加以控制。 考察了水廠(chǎng)常規(guī)處理工藝以及給水深度處理中試系統(tǒng)對(duì)水中雌、孕激素類(lèi)污染物質(zhì)的去除效果。結(jié)果表明，常規(guī)水處理單元對(duì)水中雌、孕激素的去除效果不佳�；炷恋韱卧獙�(duì)雌、孕激素的去除率不到40%，過(guò)濾對(duì)雌、孕激素的去除率不到20%，且兩個(gè)單元都出現(xiàn)了出水濃度高于進(jìn)水的情況。 臭氧對(duì)雌、孕激素有很好的去除效果，且臭氧對(duì)雌、孕激素的去除效果與臭氧投量有關(guān)，也與雌、孕激素初始濃度有關(guān)。臭氧投量為1.5~3.0mg/L時(shí)，雌激素和孕激素的去除率為90%~97%。雌激素和孕激素初始濃度較低時(shí)，去除率略有下降。通過(guò)對(duì)臭氧氧化產(chǎn)物進(jìn)行分析，發(fā)現(xiàn)臭氧并沒(méi)有將目標(biāo)污染物完全礦化。 生物活性炭單元和超濾單元單獨(dú)使用時(shí)對(duì)水中雌、孕激素的去除率低于臭氧單元。其中生物活性炭單元對(duì)E2和E3的去除率在70%左右，對(duì)E1和EE2的去除率不到20%，超濾單元對(duì)各雌激素和孕激素的去除率在65%~85%之間。高級(jí)氧化—吸附—超濾膜過(guò)濾組合工藝對(duì)雌激素和孕激素具有很好的去除效果，出水中基本沒(méi)有檢出雌激素和孕激素，說(shuō)明該工藝能很好地保證出水水質(zhì)。
[Abstract]:Estrogen and progesterone are important endocrine disruptors, and the presence of these substances in the environment may cause potential harm to ecosystem and human health. Can help to understand the water quality of Songhua River, and provide data support for related research and decision. An on-line solid phase extraction (SPE) method for the determination of estrogen and progesterone in water by UPLC-MS/MS has been developed. The detection limit of each estrogen and progesterone is 0.1 ~ 1.0ng / L, which meets the requirements of trace analysis. By sampling and analyzing the water body in Harbin section of Songhua River, It was found that the concentration range of estrogen E _ (1) E _ (2) E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (2) E _ (3) and E _ (2) E _ (2) E _ (3) and E _ (2) N. The regularity that the downstream is higher than the upstream, and the ice and snow melting period and the high water season are higher than the dry season. The concentrations of estrogen and progesterone have been increased. By comparing the concentration of E1 and E2, it is inferred that the existence of estrogen in water is closely related to human activities. The ecological risk assessment shows that the existence of E1C E2E3 and LNG in Harbin section of Songhua River has certain ecological risks, and some relevant measures should be taken. The analysis of estrogenic activity also shows that E1C E2E3 and E2E3 in Harbin reach of Songhua River have some ecological risks. The EEQ value of most sampling points in this section is higher than that of predicted unaffected concentration, and relevant measures should be taken to control it. The removal efficiency of female and progesterone pollutants in water by conventional treatment process and advanced water treatment system was investigated. The removal rate of progesterone in coagulation sedimentation unit was less than 40% for female, and less than 20% for female in filtration, and the effluent concentration was higher than that in influent in both units. Ozone has a good effect on the removal of estrogen and progesterone, and the removal effect of ozone on estrogen and progesterone is related to the amount of ozone, and also to the initial concentration of estrogen and progesterone. The removal rate of estrogen and progesterone is 90%. When the initial concentration of estrogen and progesterone is low, the removal rate decreases slightly. Through the analysis of ozonation products, it is found that ozone does not completely mineralize the target pollutant. The removal rate of progesterone in water by biological activated carbon unit and ultrafiltration unit alone was lower than that of ozone unit, and the removal rate of E2 and E3 by biological activated carbon unit was about 70%. The removal rate of E1 and EE2 was less than 20%, and the removal rate of estrogen and progesterone by ultrafiltration unit was between 65% and 85%. Estrogen and progesterone were not detected in the effluent, indicating that the process can ensure the quality of the effluent.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：TU991.2;X143

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