上海地区环境与人体介质中多溴联苯醚的污染特征及来源解析

发布时间：2018-05-15 12:20

本文选题：多溴联苯醚 + 底泥　；参考：《上海大学》2015年硕士论文

【摘要】：上海位于长江入海口,是我国工业和经济中心。近几年来,随着城市化和工业化的进一步加剧,上海市阻燃剂的生产和使用日益增多,目前有许多文献表明阻燃剂已经普遍存在于上海环境介质中。多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)是阻燃剂中使用较为广泛的一种,难降解,易富集,在环境中可长距离迁移。它还具有生物毒性,能够干扰生物的内分泌系统,可以导致神经毒性、免疫毒性、生殖毒性和肝脏毒性。本研究主要以上海市西部、东部、中部以及东南部的河流底泥为目标对象,对13种PBDEs同系物在目标介质中的污染浓度水平、组成特征和来源途径做出系统深入的研究,并对其潜在的生态风险进行评估,从而判断PBDEs对于底栖生物的影响程度。接着又以上海市嘉定区作为典型地区采集人体血清样品,初步检测分析PBDEs的污染浓度水平,比较其各个同系物所占含量。通过浓度对比来反应特定区域环境介质和人体中PBDEs污染水平关系。以下是本文得到的结果与讨论:①本研究表明PBDEs在上海市水体沉积物中广泛存在,东南部地区河流底泥中污染程度最高,浓度范围为1008.5~13087.1 pg g-1 dw,平均值为3502.59 pg g-1 dw;接着是中部地区,浓度范围为876.0~8697.8 pg g-1 dw,平均值为3113.23pg g-1 dw;西部和北部地区污染程度较低,浓度范围分别为124.0~4203.3 pg g-1dw和933.9~2184.1 pg g-1 dw,平均值分别为2567.36 pg g-1 dw和1543.96 pg g-1dw。对比国内外相关研究发现,本地区BDE-209的浓度处于中等水平,低于周围城市水体但高于台湾和南海地区。BDE-209是主要的同系物,占总量的72%以上。应用PCA对PBDEs同系物的来源进行分析,研究得出河流底泥中的PBDEs主要来源于商业用PBDEs阻燃剂产品。同时,低溴代PBDEs同系物较高的因子载荷表明高溴代PBDEs可能通过不同的降解途径转化为低溴代的PBDEs同系物。对沉积物中的PBDEs进行生态风险评估发现,PBDEs对研究地区沉积物中的底栖生物目前没有表现出明显的生态风险。不过,鉴于本地区高浓度De BDEs可能通过食物链转化为高毒性的Pe BDEs,从而有进一步提高生态风险的可能。因此,PBDEs对本研究区域水生生态系统可能造成的生态风险还需进一步研究。②本研究对人体血清中PBDEs分析方法及仪器条件进行了探索,PBDEs混合标品在仪器中的出峰时间RSD在0.01%~0.07%之间,相对比较稳定。而出峰峰面积的RSD则处于15%~22%之间,误差比较大,但仍属合理范围之内。本文研究了两种血清中PBDEs的分析方法,方法一主要利用液夜萃取提取脂肪,然后利用凝胶渗透色谱法去除大分子的脂肪,再用有机溶剂把PBDEs从脂肪中提取出来。方法一过程比较复杂,而且回收率不稳定。方法二利用固相萃取小柱来提取血清中的PBDEs,将分离、提取、净化三个步骤集中到一起,因而较为简便。而结合超声萃取则提高了溶液的萃取率,增加了回收率。方法一PBDEs混标的回收率49.2%~144.7%,两个内标的回收率为111.6%和132.4%。方法二混标的回收率范围为81.1%~117.2%,内标回收率为105.8%和114.6%。因此采用方法二来进行PBDEs的前处理实验。检测上海市特定地区人体血清样品平均浓度为6.677ng/g,浓度范围0.545~26.743 ng/g,说明此类物质在血清中广泛存在。PBDEs同系物中六溴联苯醚所占比例普遍比较高,接着是五溴和七溴。与国内外人体血清PBDEs浓度相比较时,本文研究对象嘉定区人体血清样品的污染浓度处于中底水平,与西班牙梅诺卡岛,印第安纳州和澳大利亚相差不多,远低于中国大连地区。③本文探讨了上海市环境与人体介质中PBDEs的污染特征及来源解析,河流底泥中的浓度范围为0.124~13.09 ng/g,其中BDE-209占PBDEs同系物总量的72%以上,人体血清中的浓度范围0.545~26.743 ng/g,其中BDE-153,BDE-154所占比例最高。可知底泥与血清中PBDEs的浓度数量级相同,但是主要同系物并不相同。结合本课题组其他研究者的研究内容,上海市其他环境介质如室内、外灰尘,土壤中的PBDEs的浓度均高于底泥,而其主要同系物都是BDE-209。他们可能都是来源于工业应用PBDEs产生的污染,并在各种环境介质中迁移转化。而环境中高溴代PBDEs进入人体时,可能在人体代谢过程中转化为低溴代物而富集在血清中,因而血清中检测到的是高浓度的六溴联苯醚。
[Abstract]:Shanghai, located at the mouth of the Yangtze River, is the center of industry and economy in China. In recent years, with the further intensification of urbanization and industrialization, the production and use of flame retardants in Shanghai are increasing. At present, there are many documents showing that flame retardants are commonly found in the environmental media of Shanghai. Polybrominated diphenyl ethers (Polybrominated diphenyl ethers, PBDEs) It is a widely used flame retardant, difficult to degrade, easily rich, and can migrate long distances in the environment. It also has biological toxicity, can interfere with biological endocrine system, and can lead to neurotoxicity, immunotoxicity, reproductive toxicity and liver toxicity. This study mainly consists of river sediment in Western Shanghai, Eastern, central and southeast parts of the city. For the target, a systematic and thorough study of the level of pollution concentration, composition characteristics and sources of 13 kinds of PBDEs homologues in the target medium was made, and the potential ecological risks were evaluated to determine the extent of the impact of PBDEs on benthos. Then, the human serum samples were collected from Jiading District in Shanghai as a typical area. A preliminary analysis of the level of PBDEs pollution concentration and comparison of the content of their homologues. The relationship between the specific regional environmental media and the level of PBDEs pollution in the human body is compared. The following are the results and discussions in this paper: (1) this study shows that PBDEs exists widely in the water sediments of Shanghai, and the rivers in the southeast region The level of pollution is the highest, the concentration range is 1008.5~13087.1 PG g-1 DW, the average value is 3502.59 PG g-1 DW, followed by the central region, the concentration range is 876.0~8697.8 PG g-1 DW, the average value is 3113.23pg, and the level of pollution is low in the western and northern regions. The average value of 2567.36 PG g-1 DW and 1543.96 PG g-1dw. compared domestic and foreign studies found that the concentration of BDE-209 in the region is at the middle level, lower than the surrounding city water, but higher than that of Taiwan and the South China Sea area.BDE-209 is the main homologue, accounting for more than 72% of the total amount. The application of PCA to the origin of PBDEs homologues is analyzed and the river is studied. PBDEs in the sediment is mainly derived from commercial PBDEs flame retardant products. At the same time, the high factor load of low brominated PBDEs homologues indicates that high brominated PBDEs may be transformed into a low brominated PBDEs homologue through different degradation pathways. The ecological risk assessment of PBDEs in the sediments found that PBDEs is the bottom of the sediments in the study area. There is no obvious ecological risk at present. However, in view of the possibility that high concentrations of De BDEs in the region may be transformed into highly toxic Pe BDEs through the food chain, it is possible to further improve the ecological risk. Therefore, further study on the possible ecological risks caused by the aquatic ecosystem in this area is further studied by PBDEs. The PBDEs analysis method and the instrument conditions in human serum are explored. The peak time of the PBDEs mixed standard in the instrument is RSD between 0.01%~0.07% and relatively stable. The RSD of the peak peak area is between 15%~22%, and the error is relatively large, but it is still within the reasonable range. This paper studies the analysis method of the PBDEs in two kinds of serum. One mainly uses liquid night extraction to extract fat, then use gel permeation chromatography to remove the fat of large molecules and extract PBDEs from fat with organic solvent. The process is complex and the recovery is unstable. Method two using solid phase extraction column to extract PBDEs in blood, separation, extraction and purification of three steps. The extraction rate of the solution was increased and the recovery rate was increased with the combination of ultrasonic extraction. The recovery rate of a PBDEs mixed standard was 49.2%~144.7%, the recovery rate of the two internal standard was 111.6%, the recovery rate of the two mixed standard was 81.1%~117.2%, the recovery rate of internal standard was 105.8% and 114.6%. was two. Therefore, the method two was adopted. The preprocessing experiment of PBDEs was carried out. The average concentration of human serum samples in the specific areas of Shanghai was 6.677ng/g, and the concentration range was 0.545~26.743 ng/g. It showed that the proportion of six brominated diphenyl ethers in the.PBDEs homologues in the serum was generally high, followed by five bromine and seven bromine. The concentration of PBDEs in human serum at home and abroad. In comparison, the pollution concentration of human serum samples in Jiading District is in the middle level, which is not much different from that of Menorca, Indiana and Australia in Menorca, Indiana and Australia. (3) this paper discusses the pollution characteristics and source analysis of the environment and the human medium in Shanghai, and the concentration model in the sediment of the river. 0.124~13.09 ng/g, of which BDE-209 accounts for more than 72% of the total PBDEs homologue, and the concentration range of human serum 0.545~26.743 ng/g, of which BDE-153, BDE-154 is the highest. It is known that the sediment is the same as the concentration of PBDEs in the serum, but the main homologues are not the same. The concentration of PBDEs in other environmental media such as indoor, outside dust, and soil is higher than the bottom mud, and the main homologue of the PBDEs is BDE-209.. They may all be derived from the pollution produced by industrial application of PBDEs and migrate in various environmental media. And when the high brominated PBDEs enters the human body, it may be transferred to human metabolism. As a low bromine substance, it is enriched in serum, so high concentration of six brominated diphenyl ethers is detected in serum.

【学位授予单位】：上海大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X502

【参考文献】