發(fā)布時間：2018-04-27 02:12

  本文選題：多氯聯(lián)苯 + 來源解析�。� 參考：《中國海洋大學(xué)》2014年博士論文

【摘要】：自1970s發(fā)現(xiàn)其毒性以來，多氯聯(lián)苯（PCBs）在環(huán)境中的含量以及其遷移轉(zhuǎn)化一直是研究的熱點(diǎn)。PCBs作為一種典型的持久性有機(jī)污染物，其來源與人類生產(chǎn)活動密切相關(guān)。在本研究中，我們選擇受陸源輸入影響較明顯的黃、東海作為研究對象，通過分析該區(qū)域沉積物中PCBs的含量、組成及分布來揭示陸架海生態(tài)環(huán)境受陸源輸入的有機(jī)污染物的影響情況。 本論文通過對該區(qū)域中66個表層沉積物樣品和4根沉積柱中PCBs的含量及組成分析，結(jié)合統(tǒng)計學(xué)模型對PCBs的來源進(jìn)行解析。主要在以下幾方面取得了一些進(jìn)展和新的認(rèn)識： (1).將超聲輔助堿液分解雜質(zhì)與溶劑萃取相結(jié)合，建立了一種快速高效凈化、萃取沉積物中多氯聯(lián)苯（PCBs）的氣相色譜分析方法。超聲輔助條件下，，在2.0mol L-1的NaOH甲醇溶液中超聲10min，利用NaOH甲醇溶液的堿解作用即可使有機(jī)氯農(nóng)藥（OCPs）完全分解，在利用有機(jī)溶劑萃取沉積物中PCBs的同時消除OCPs等的干擾。在優(yōu)化的實(shí)驗(yàn)條件下，PCBs各單體的回收率在72.1%－113.7%，相對標(biāo)準(zhǔn)偏差在0.4%－6.3%(n=6)之間。氣相色譜圖顯示，堿解凈化后雜質(zhì)含量顯著減少，基線得以明顯改善，能滿足定性定量檢測的要求。 (2).東海內(nèi)陸架泥質(zhì)區(qū)表層沉積物中PCBs含量為24.3~343.3pg/g，平均126.7pg/g，濃度高值出現(xiàn)在長江口附近區(qū)域。單體組成以3Cl-5Cl CBs為主，占76.1%；含氯量45.1%-58.8%，平均49.9%，單體組成特征與國產(chǎn)PCBs的單體組成較為相似；雖然PCBs濃度在河口區(qū)出現(xiàn)高值，但含氯量較低，隨離長江口距離增加，含氯量有增加趨勢。該區(qū)域表層沉積物中PCBs的分布呈現(xiàn)明顯的來源控制特征，表明長江可能是該區(qū)域中PCBs的主要輸入源。 (3).黃海中部區(qū)域表層沉積物中PCBs含量為99pg/g~3.13ng/g，平均715pg/g，濃度高值主要出現(xiàn)在36°N斷面附近。5Cl CBs含量顯著偏高，占43.70%；沉積物中PCBs的含氯量介于47.64%~58.15%,平均53.45%，與東海內(nèi)陸架泥質(zhì)區(qū)相比，該區(qū)域沉積物中PCBs的含氯量較高，高氯取代單體含量所占比重顯著偏高。該區(qū)域表層沉積物中PCBs的分布受控于沉積環(huán)境，河流輸送的PCBs可能對該區(qū)域中PCBs的含量貢獻(xiàn)較少。 (4).對比了主成分分析-多元線性回歸（PCA-MLR）與偏最小二乘回歸（PLSR）的源解析結(jié)果。兩種方法能夠給出相近的成分載荷，主成分1（PC1）相似度較高，但其他成分樣本得分相差較大，其結(jié)果表明PLSR所解析結(jié)果更加精細(xì)和便于識別。基于PLSR的解析結(jié)果，東海內(nèi)陸架泥質(zhì)區(qū)表層沉積物中的PCBs64.4%來源于地表徑流輸送入海的工業(yè)合成PCBs（3Cl CBs占主導(dǎo)），21.8%來源于大氣沉降（5ClCBs占主導(dǎo)），13.8%來源于沿岸城市排污（高氯取代為主）；黃海表層沉積物中的PCBs60.5%來源于大氣沉降輸送的非故意產(chǎn)生的PCBs；24.0%來源于國產(chǎn)5Cl CBs，15.5%來源于經(jīng)河流輸送入海的3Cl CBs。 (5).近一個世紀(jì)以來，長江口區(qū)域PCBs的沉積記錄受PCBs的生產(chǎn)使用影響明顯，濃度峰值出現(xiàn)在1950s-1960s；在近代PCBs的含量有逐漸增高的趨勢。近百年來東海內(nèi)陸架泥質(zhì)區(qū)所沉積的PCBs中大部分（＞70%）來源于工業(yè)合成的PCBs泄漏，人為活動中非故意產(chǎn)生的PCBs所占比例較少；據(jù)PLSR結(jié)果，在近幾十年工業(yè)合成的PCBs對該區(qū)域中PCBs的影響程度有增加趨勢，而非故意產(chǎn)生的PCBs影響程度并無明顯的變化趨勢，說明非故意過程中PCBs的形成受多種因素的影響，其產(chǎn)生量與工業(yè)生產(chǎn)總值并不是簡單的線性關(guān)系。
[Abstract]:Since 1970s has been found to be toxic, the content of polychlorinated biphenyls (PCBs) in the environment and its migration and transformation have always been the focus of research,.PCBs as a typical persistent organic pollutant. Its source is closely related to human production activities. In this study, we choose the yellow and East China Sea as the research object, which is influenced by land source input. By analyzing the content, composition and distribution of PCBs in the sediments of this area, we can reveal the influence of the organic pollutants from the terrigenous source on the ecological environment of the shelf sea.
Based on the analysis of the content and composition of PCBs in 66 surface sediment samples and 4 sedimentary columns in this area, the source of PCBs is analyzed with statistical model. Some progress and new understanding are made in the following aspects:
(1) a rapid and efficient purification method for the extraction of polychlorinated biphenyls (PCBs) in sediments was established by combining the ultrasonic assisted lye decomposition impurities and solvent extraction. The ultrasonic 10min was used in the NaOH methanol solution of the 2.0mol L-1 under the ultrasonic assisted condition, and the organochlorine pesticide (OCPs) could be finished by the alkali solution of NaOH methanol solution. Full decomposition, in the use of organic solvent extraction of PCBs in the sediment at the same time elimination of OCPs interference. Under the optimized experimental conditions, the recovery of PCBs monomers is 72.1% - 113.7%, the relative standard deviation is between 0.4% and 6.3% (n=6). Gas chromatography shows that the content of impurities in the alkaline solution is significantly reduced, the baseline is obviously improved and can be satisfied. The requirements for the quantitative detection of sex.
(2) the content of PCBs in the surface sediments of the muddy area of the East China Sea is 24.3~343.3pg/g, with an average of 126.7pg/g and high concentration in the vicinity of the Yangtze Estuary. The composition of the monomer is mainly 3Cl-5Cl CBs, accounting for 76.1%, the chlorine content is 45.1%-58.8%, and the average composition is similar to that of the homemade PCBs, although the PCBs concentration is in the estuary area. There is a high value, but the chlorine content is low. With the increase of the distance from the Yangtze Estuary, the chlorine content increases. The distribution of PCBs in the surface sediments of this region shows a distinct source control feature, indicating that the Changjiang River may be the main source of PCBs in this area.
(3) the content of PCBs in the surface sediments of the central the Yellow Sea region is 99pg/g~3.13ng/g, with an average of 715pg/g, and the high concentration of the concentration is mainly higher in the vicinity of the 36 degree N section, and the content of.5Cl CBs is 43.70%. The chlorine content of PCBs in the sediments is between the 47.64%~58.15% and the average of 53.45%. The content of PCBs in the sediments of the East China Sea is compared with the mud content in the East China Sea. The proportion of PCBs in the surface sediments of this region is controlled by the sedimentary environment, and the PCBs transported by the river may contribute less to the content of PCBs in this area.
(4) compared the source analysis results of principal component analysis multivariate linear regression (PCA-MLR) and partial least squares regression (PLSR). The two methods can give similar component loads, the similarity of principal component 1 (PC1) is higher, but the scores of other components are different, and the results show that the PLSR results are more precise and easier to recognize. PLSR based on the results. The analytical results show that PCBs64.4% from the surface sediments of the muddy area of the East China Sea inland shelf is derived from the industrial synthetic PCBs (dominated by 3Cl CBs) transported to the sea by surface runoff. 21.8% originates from atmospheric sedimentation (5ClCBs dominated) and 13.8% from coastal city discharge (high chlorine substitution), and the PCBs60.5% in the surface sediments of the Yellow Sea is derived from atmospheric sedimentation. The unintentional PCBs; 24% came from the domestic 5Cl CBs, and 15.5% came from the 3Cl CBs. transported to the sea through the river.
(5) (5) the deposition records of the Yangtze Estuary region have been affected by the production and use of the PCBs in the last century. The peak concentration appears at 1950s-1960s, and the content of PCBs in modern times is increasing gradually. Most of the (> 70%) of the PCBs deposited in the mud area of the inland shelf of the East China Sea in the last hundred years is derived from the industrial synthesis of PCBs leakage and human activities. The proportion of unintentionally produced PCBs is less; according to the results of PLSR, the impact degree of industrial synthetic PCBs on PCBs in this area has increased in recent decades, and the degree of unintentionally produced PCBs has no obvious change trend. It shows that the formation of PCBs in unintentional process is influenced by many factors, and its production amount and industrial production are general. Value is not a simple linear relationship.

【學(xué)位授予單位】：中國海洋大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：X55

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