本文關(guān)鍵詞：供水管網(wǎng)中氯胺作用下內(nèi)分泌干擾物的遷移轉(zhuǎn)化機(jī)理研究　出處：《浙江大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 給水管網(wǎng) 氯胺消毒 EDCs降解 降解產(chǎn)物 雌激素活性

【摘要】：近年來,伴隨著工業(yè)的迅速發(fā)展和人民生活水平的提高,水環(huán)境的污染問題也日益突出,人們對飲用水安全的關(guān)注也越來越多。同時,檢測技術(shù)的進(jìn)步,使得水體中越來越多的內(nèi)分泌干擾物(EDCs)被檢測出來,研究證明EDCs會對水體中的生物產(chǎn)生雌激素效應(yīng)。此外,氯胺消毒是通常采用的一種飲用水消毒方式,但是對于氯胺作用下EDCs在城市供水過程中的遷移轉(zhuǎn)化機(jī)理的研究尚未見報道。本文以長期存在于水體中的雌二醇(E2)、雌三醇(E3)和雙酚A(BPA)為研究對象,利用浙江大學(xué)玉泉校區(qū)中試管網(wǎng)實(shí)驗(yàn)平臺為研究手段,系統(tǒng)研究了氯胺作用下三種EDCs在城市供水管網(wǎng)中的降解影響因素,產(chǎn)物生成情況以及降解過程中水體生物毒性的變化情況。為了確定后續(xù)EDCs降解所采用的氯氮比(Cl/N)以及氯胺濃度,本研究首先考察了不加EDCs的情況下,氯胺的生成和衰減情況。對不同Cl/N下氯胺的生成情況進(jìn)行研究發(fā)現(xiàn):Cl/N介于1-14之間時,自由氯、一氯胺和總有效氯在不同水質(zhì)條件下的生成趨勢均為去離子水主體水中試管網(wǎng);而對于二氯胺,在中試管網(wǎng)中的生成量遠(yuǎn)高于去離子水中的生成量,且在Cl/N為10時,中試管網(wǎng)中二氯胺濃度占總有效氯濃度的90%以上。對不同Cl/N下氯胺的衰減情況進(jìn)行研究發(fā)現(xiàn),球墨鑄鐵管中各種形態(tài)的氯胺在不同Cl/N下的衰減趨勢相同,一氯胺在不同Cl/N下的衰減速率為6:13:14:15:1,隨著反應(yīng)的進(jìn)行,二氯胺濃度先增大后減小,且這種變化與Cl/N沒有明顯的相關(guān)性;此外,一氯胺在不同管材中的衰減速率為不銹鋼管PE管球墨鑄鐵管,二氯胺的濃度在不同管材中均先增大后減小,且增大趨勢為不銹鋼管PE管球墨鑄鐵管。通過對EDCs在去離子水和中試管網(wǎng)中的降解規(guī)律的研究發(fā)現(xiàn),不同Cl/N下,EDCs在去離子水和中試管網(wǎng)中降解區(qū)別較大,具體表現(xiàn)為在Cl/N為3和4時,反應(yīng)9h,EDCs在去離子水中的去除率小于30%,而在管網(wǎng)中,EDCs的去除率在70%以上,這主要是由于不同水體條件下,反應(yīng)體系中NH2Cl和NHCl2所占的比例不同造成的。此外,增加初始總有效氯的濃度、升高溫度、提高反應(yīng)體系的pH和增加管網(wǎng)中水流流速均可加快EDCs的降解。但是,當(dāng)反應(yīng)體系中溴離子濃度介于0-80μg/L時,溴離子濃度的變化對EDCs的降解幾乎沒有影響。不同管材下,EDCs的降解速率為球墨鑄鐵管PE管不銹鋼管,這是管垢,水體pH、氯胺含量共同作用的結(jié)果。對不同水質(zhì)條件下EDCs的降解發(fā)現(xiàn),主體水有機(jī)物和管壁本身并不影響EDCs的降解,在加氯胺的情況下,才會對EDCs的降解產(chǎn)生影響,且影響均是負(fù)面的,即主體水有機(jī)物和管壁的存在均不利于EDCs的降解。此外,利用GC-MS首次對氯胺消毒下EDCs降解的中間產(chǎn)物進(jìn)行了檢測。其中,E2的檢測中共檢測到10種中間產(chǎn)物,且第一次檢測到E2的含氮副產(chǎn)物。分析發(fā)現(xiàn)氯胺消毒情況下,E2的反應(yīng)發(fā)生在苯環(huán)、C9和C17上,主要為苯環(huán)酚羥基臨位的取代反應(yīng)、消去反應(yīng)和加氫反應(yīng)。E3的檢測中共檢測到9種中間產(chǎn)物,其中E2和2-氯-E3是兩種主要的中間產(chǎn)物,說明親電取代反應(yīng)是E3氯胺消毒過程中的主要反應(yīng)。BPA的檢測中共檢測到12種中間產(chǎn)物,且第一次檢測到BPA的含氮副產(chǎn)物,在氯胺作用下,BPA的反應(yīng)主要為苯環(huán)酚羥基臨位的親電取代反應(yīng),包括氯取代、溴取代以及N02的取代。三種EDCs的降解中均沒有檢測到開環(huán)的產(chǎn)物。對EDCs在氯胺作用下的生物毒性檢測發(fā)現(xiàn):隨著反應(yīng)時間的增加,反應(yīng)體系的雌激素活性先升高后降低,最后趨于穩(wěn)定。降解反應(yīng)的前期,水體的雌激素活性大于同時刻空白對照實(shí)驗(yàn)的雌激素活性,說明EDCs濃度的下降可能并不意味著其雌激素活性的下降,中間產(chǎn)物的雌激素活性可能強(qiáng)于母體分子的雌激素活性。因此,對EDCs降解過程中雌激素活性的評估,應(yīng)該明確消毒時間,并且在去除污染物的同時,也要采取必要措施減少消毒工過程中中間產(chǎn)物的生成。
[Abstract]:In recent years, with the rapid development of industry and the improvement of people's living standard, the problem of water pollution has become increasingly prominent, people pay attention to the safety of drinking water is also increasing. At the same time, detection technology, making more and more water in the endocrine disruptors (EDCs) were detected, studies have shown that EDCs can produce estrogen effect of water organisms. In addition, Chloraminated drinking water disinfection is a commonly used method, but for the study of migration and transformation mechanism in city water supply in the process of chloramine EDCs under the action has not been reported. In this paper, persist in the water in the estradiol (E2), female three alcohol (E3) and bisphenol A (BPA) as the research object, using the experimental platform of Zhejiang University campus network Jade Spring tube as the research means, research the influence factors of the degradation system under three kinds of chloramine EDCs role in city water supply network, product formation The changes of water and biological toxicity of the degradation process. In order to determine the chlorine nitrogen ratio with subsequent degradation of EDCs (Cl/N) and chloramine concentration, this study first investigated the absence of EDCs, chloramine generation and attenuation of Cl/N under different conditions to generate chloramine Cl/N between the study found: 1-14, free chlorine, monochloramine and production trends of the total active chlorine in different water conditions were deionized water body water tube net; and for the two generation of chloramine, generation in tube network is much higher than that of deionized water, and when the Cl/N is 10, in the tube network two chloramine the concentration of effective chlorine concentration accounted for more than 90%. The study found that the attenuation of different Cl/N chloramine, the attenuation trend of nodular cast iron pipe chloramine in various forms in different Cl/N under the same, the decay rate of monochloramine under different Cl/N 6:13:14:15:1, as the reaction proceeds, two chloramine concentration increased first and then decreased, and the change of Cl/N with no obvious correlation; in addition, the decay rate of monochloramine in different pipe cast iron pipe for stainless steel pipe ductile, the concentration of two chloramine increased firstly in different pipe and then decreased, and increased trend stainless steel pipe ductile iron pipe. Through the research on the degradation of EDCs in deionized water and in vitro in the network found that under different Cl/N, EDCs in deionized water and in vitro degradation in the net difference is bigger, the specific performance in Cl/N was 3 and 4, the reaction of 9h, the removal rate of EDCs in deionized water less than 30%, while in the network, the EDCs removal rate is over 70%, which is mainly due to the different water conditions in the reaction system of NH2Cl and NHCl2 in the proportion of different causes. In addition, increase the concentration of effective chlorine, total initial temperature, extraction The high pH of the reaction system and increase the network flow velocity could accelerate the degradation of EDCs. However, when the concentration of bromide ion in the reaction system between 0-80 g/L, bromide concentration degradation of EDCs has almost no effect. Different pipes, the degradation rate of EDCs for ductile iron PE tube stainless steel tube, the is the pipe scale, water pH, interaction results. The degradation of chloramine content under different water quality EDCs, the main water organic matter and the wall itself does not affect the degradation of EDCs, in the case of the influence of chloramine, the degradation of EDCs and will influence is negative, which is the main water the organic matter and the pipe wall are not conducive to the degradation of EDCs. In addition, the use of GC-MS for the first time on EDCs degradation of chloramine disinfection under the intermediate products were detected. The detection of E2 were detected in 10 kinds of intermediate products, and the first detected nitrogen by-products containing E2 Analysis shows that chloramine disinfection conditions, E2 reaction occurs in the benzene ring, C9 and C17, mainly for the benzene hydroxyl substitution reaction on the elimination reaction and hydrogenation reaction of.E3 detection were 9 kinds of intermediate products, including E2 and 2- chloride -E3 are two main intermediate products, to illustrate the pro the electrical substitution reaction is the main reaction.BPA E3 chloramine disinfection in the process of detection were 12 kinds of intermediate products, and the first detected nitrogen byproducts containing BPA, chloramine in under the action of the BPA reaction was benzene phenol hydroxyl adjacent electrophilic substitution reaction, including chlorine, bromine and N02 replace. Degradation of three EDCs in the products were not detected. The open loop found on the ecotoxicity of EDCs in chloramine under the action: with the increase of reaction time, the reaction system of the estrogenic activity increased first and then decreased, and finally tends to be stable. The degradation reaction, Estrogenic activity of water is greater than the time control estrogen activity experiment, that the decline in the concentration of EDCs may not mean the decline of estrogen activity, the estrogenic activity of estrogenic activity of intermediates may be stronger than the parent molecule. Therefore, the evaluation of the estrogenic activity of EDCs in the degradation process, should clear the disinfection time, and in the removal of pollutants at the same time, to take the necessary measures to reduce the formation of intermediate products in the process of disinfection work.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TU991.33

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