【摘要】：短鏈氯化石蠟(SCCPs)是一類組成復雜,具有遠距離遷移、環(huán)境持久性、生物蓄積性和一定的生物毒性,已被列入《關于持久性有機污染物的斯德哥爾摩公約》受控名單。我國是氯化石蠟生產(chǎn)和使用最多的國家,且尚未限制SCCPs的生產(chǎn)。短鏈氯化石蠟(short-chain chlorinated paraffins,SCCPs)是碳鏈長度為10-13,氯原子取代數(shù)為1-13個的正構烷烴衍生物。工業(yè)上短鏈氯化石蠟是由氯氣與正構烷烴反應合成,因此生產(chǎn)出的短鏈氯化石蠟是由數(shù)以萬計的同系物和同分異構體組成的混合物,氯代程度通常為30%~70%(以質(zhì)量計算)。目前文獻多采用氣相色譜負化學源質(zhì)譜法進行環(huán)境中短鏈氯化石蠟的測定,發(fā)現(xiàn)環(huán)境中短鏈氯化石蠟普遍存在。本文首先對SCCPs商業(yè)標準品的組成進行了測定分析,結(jié)果表明:氯含量63%C10-13 SCCPs標準品中,氯代的C10、C11、C12、C13的百分組成分別為10.1%、33.8%、33.1%、23%;Chloroparaffin C10 65.02%Cl中主要以7氯代和8氯代化合物為主,分別占34%和38%;Chloroparaffin C11 65.25%Cl主要以8氯代和9氯代化合物為主,分別占40%和32%;Chloroparaffin C1269.98%Cl中主要以9氯代和10氯代化合物為主,分別占37%和35%;Chloroparaffin C1365.18%Cl中主要以9氯代化合物為主,占50%左右。對我國白洋淀水和沉積物中的短鏈氯化石蠟進行分析研究結(jié)果表明:白洋淀水中SCCPs濃度范圍為1562.8~56 305.9 ng/L,平均值為7223ng/L,中值為3168.9ng/L;沉積物中SCCPs的濃度范圍在1270~254203ng/g(干重)之間,平均值為24454ng/g,中值為3458ng/g。經(jīng)分析白洋淀水和沉積物中短鏈氯化石蠟的污染趨勢基本一致�？偟膩碚f,白洋淀15個采樣點的水和沉積物均有SCCPs的檢出,檢出率為100%,主要以碳鏈C10和C11的六氯和七氯的SCCPs為主要同類物。主成分分析結(jié)果表明:白洋淀沉積物中主要以C10H15Cl7、C10H15Cl7、C12H13Cl9、C13H14Cl8、C11H16Cl6、C12H16Cl6、C13H16Cl6為污染特征。和國內(nèi)外相比白洋淀污染水平較高。長江流域是我國經(jīng)濟發(fā)展水平和城鎮(zhèn)化水平較高的地區(qū)之一,隨著經(jīng)濟的發(fā)展,大量的生活污水和工業(yè)廢水排入長江,污染日趨嚴重,所以本文采集了長江中游的水和沉積物,并進行了SCCPs的污染特征研究。所有的采樣點均有短鏈氯化石蠟檢出,檢出率為100%。測的水中SCCPs濃度范圍在1131~65640ng/L之間,平均濃度為18989ng/L,中值為14691ng/L。沉積物濃度范圍在251.9-397600.4ng/g(干重)之間,平均濃度為54512ng/g,中值濃度為2363.7ng/g。長江中上游的污染水平要低于長江中下游的污染水平,其中長江14、長江15、長江21以及長江5中的短鏈氯化石蠟含量較高,主要以鏈長C10和C13的六氯的SCCPs為主要同類物。沉積物的中值粒徑和SCCPs的污染水平?jīng)]有相關性;沉積物中有機質(zhì)SCCPs的濃度呈正相關。過濾膜中短鏈氯化石蠟的濃度范圍在1868ng/L~513335.9ng/L之間,平均值為64219ng/L,中值為8211ng/L。與國外相比污染水平較高。長江中游主成分主要來自六氯和十氯代的短鏈氯化石蠟。
[Abstract]:Short chain chlorinated paraffins (SCCPs) are a class of complex SCCPs with long distance transport, environmental persistence, bioaccumulation and certain biotoxicity, which have been included in the Stockholm Convention on persistent Organic pollutants (pops) controlled list. The production and use of chlorinated paraffin is the most in China, and the production of SCCPs has not been restricted. Short chain chlorinated paraffins (short-chain chlorinated paraffins SCCPs) are n-alkane derivatives with carbon chain length of 10-13 and chlorine atom substitution number of 1-13. Industrial SCCPs are synthesized by the reaction of chlorine gas with n-alkanes, so the SCCPs produced are a mixture of tens of thousands of homologues and isomers, and the chlorination degree is usually 30% (by mass). At present, gas chromatography negative chemical source mass spectrometry is used to determine SCCPs in the environment, and it is found that SCCPs are ubiquitous in the environment. In this paper, the composition of SCCPs commercial standard was determined and analyzed. The results showed that in the 630-13 SCCPs standard of chlorine content, the percentage composition of chlorinated C10C11C11C12C13 was 10.1% and 33.833.833.1%, respectively. In the 65.02%Cl of Chloroparaffin C10, it was mainly composed of 7 chlorinated compounds and 8 chlorinated compounds. Chloroparaffin C11 65.25%Cl was mainly composed of 8 chlorinated compounds and 9 chlorinated compounds, 40% and 32% Chloroparaffin C1269.98%Cl were mainly 9 chlorinated compounds and 10 chlorinated compounds, respectively, and 37% and 35% Chloroparaffin C1365.18%Cl were mainly 9 chlorinated compounds, accounting for 50% or so. The results of analysis of SCCPs in Baiyangdian water and sediments in China show that the concentration of SCCPs in Baiyangdian water is in the range of 1562.8N 56 305.9 ng / L, the average value is 7223 ng / L, the median is 3168.9 ng / L, and the concentration of SCCPs in sediments is in the range of 1270~254203ng/g (dry weight). The average is 24454 ng / g, and the median is 3458 ng / g. The pollution trend of SCCPs in Baiyangdian water and sediment was basically consistent. In general, SCCPs was detected in water and sediment of 15 sampling sites in Baiyangdian, and the detection rate was 100. The main congeners were hexachloro and SCCPs of carbon chain C10 and C11 and heptachlor. The results of principal component analysis show that the main pollution characteristics in Baiyangdian sediments are C10H15Cl7, C10H15Cl7, C12H13Cl9, C13H14Cl8, C11H16Cl6, C12H16Cl6, C13H16Cl6. Compared with the domestic and foreign Baiyangdian pollution level is higher. The Yangtze River Valley is one of the areas with high level of economic development and urbanization. With the development of economy, a large amount of domestic sewage and industrial wastewater are discharged into the Yangtze River, and the pollution is becoming more and more serious. So, this paper collected the water and sediment from the middle reaches of the Yangtze River. The pollution characteristics of SCCPs were studied. SCCPs were detected in all sampling sites and the detection rate was 100%. The range of SCCPs concentration in water is between 1131~65640ng/L and the average concentration is 18989ng / L and the median is 14691ng / L. The sediment concentration is in the range of 251.9-397600.4ng/g (dry weight), the average concentration is 54512ng / g, the median concentration is 2363.7ng / g. The pollution level in the upper and middle reaches of the Yangtze River is lower than that in the middle and lower reaches of the Yangtze River. The SCCPs in the Yangtze River 14, Yangtze River 15, Changjiang 21 and Yangtze River 5 are higher, with the SCCPs of chain length C10 and C13 as the main congeners. There was no correlation between the median particle size of sediment and the pollution level of SCCPs, but there was a positive correlation between the concentration of SCCPs in organic matter and the concentration of SCCPs in sediment. The concentration of SCCPs in the filtration membrane was in the range of 1868ng/L~513335.9ng/L, with an average of 64219ng / L and a median value of 8211ng / L. Compared with foreign countries, the level of pollution is higher. The main components in the middle reaches of the Yangtze River mainly come from HCH and chlordated short chain chlorinated paraffins (SCCPs).
【學位授予單位】：河北師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X592

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