新型溴代阻燃剂在黄河三角洲湿地沉积物中的分布及储量分析研究

发布时间：2018-12-08 16:18

【摘要】：随着持久性有机污染物的大量使用,环境问题变的越来越严重。一些国家和国际组织开始禁止或者限制它们的生产和使用,例如:多溴联苯醚(PBDEs)和多氯联苯(PCBs)。然而,一些新型的溴代阻燃剂(BFRs)开始出现,例如:三(2,3二溴丙基)异氰脲酸酯(TBC)、六溴环十二烷(HBCDs)、四溴双酚A(TBBPA),它们被大量应用于石油化工业、机械制造业、电子电器产品制造业中,研究表明它们具有类似于持久性有机污染物(POPs)的性质,并广泛分布于环境中。本文以黄河三角洲湿地为环境模型,研究该湿地沉积物中TBC和HBCDs的污染水平、组成特征、与TOC之间相关性、储量估计以及暴露风险等。论文的主要内容与结论如下:1.本实验优化了TBC和HBCDs前处理及分析检测方法,对样品进行冷冻干燥、索氏提取、过复合硅胶层析柱、旋转蒸发及氮吹浓缩,最后进UPLC-MS-MS分离检测。为保证实验精确度,进行样品加标回收实验,所有样品中均加入同位素标记的[13C12]-α-、β-、γ-HBCD作为回收率内标,回收率分别为88 102%、93 107%、83 98%,相对标准偏差(RSD)的范围是4.73 9.11%。2.实验结果表明:TBC的检出率为100%,含量在0.20-29.03 ng·g-1之间,平均含量为6.88 ng·g-1;α-、β-、γ-HBCD的检出率分别为75%、71%、96%,平均含量分别为0.69 ng·g-1、0.42 ng·g-1、5.20 ng·g-1;α-、β-、γ-HBCD所占的比例分别为10.1%(5.7 17.0%)、6.1%(3.0 12.1%)、83.8%(73.2 100.0%)。3.黄河口处采样点HBCDs平均含量(10.46 ng·g-1)相对其他点较高,沿黄河故道采样点TBC和HBCDs的含量较低。可能是黄河改道上游的污染不流经黄河故道,也不会随着径流的泥沙携带而沉积,并且政府出台了保护黄河故道的政策。另外,空气进行远距离传输是TBC、HBCDs迁移的方式之一,但主要的污染方式还是点源污染。4.用SPSS 17.0对检测结果进行分析(1)对TBC和HBCDs进行相关性分析表明:HBCDs三种同分异构体之间显著相关,TBC与HBCDs各同分异构体之间存在弱相关,这表明TBC与HBCDs的污染源可能存在一定的区别。(2)TOC与TBC、HBCDs呈弱的正相关性,TOC与TBC,α-HBCD,β-HBCD,γ-HBCD,ΣHBCDs含量相关系数分别为:r=0.154(p=0.473),r=0.138(p=0.522),r=0.02(p=0.917),r=0.295(p=0.162),r=0.275(p=0.194)。这一结果表明:沉积物中总有机碳含量是影响BFRs分布的因素之一。(3)对黄河三角洲湿地沉积物中TBC、α-、β-、γ-HBCD和ΣHBCDs进行储量估计,并对TBC和HBCDs的暴露途径包括职业暴露和非职业暴露(饮食暴露、吸吸暴露、皮肤摄入等)进行分析。(4)为进一步了解黄河三角洲湿地沉积物中TBC和HBCDs的水平,将该区域与胶州湾湿地进行对比,结果表明:TBC含量约高于胶州湾湿地2倍,HBCDs的含量稍低于胶州湾湿地。在与世界其它地区对比中发现,黄河三角洲湿地HBCDs的含量(8.40 ng?g-1)处于中等水平。
[Abstract]:With the extensive use of persistent organic pollutants, environmental problems become more and more serious. A number of countries and international organizations have begun to ban or restrict their production and use, such as polybrominated diphenyl ether (PBDEs) and polychlorinated biphenyls (PCBs).) However, some new brominated flame retardants, (BFRs), have begun to emerge, such as tris (2br 3 dibromopropyl) isocyanurate (TBC), hexabromocyclododecane (HBCDs), tetrabromobisphenol A (TBBPA), which are widely used in the petrochemical industry. Mechanical manufacturing, electronic and electrical products manufacturing industry, research shows that they have the properties similar to the persistent organic pollutant (POPs), and they are widely distributed in the environment. Taking the wetland in the Yellow River Delta as an environmental model, the pollution level, composition, correlation with TOC, reserve estimation and exposure risk of TBC and HBCDs in the sediments of the wetland are studied in this paper. The main contents and conclusions are as follows: 1. In this experiment, the pretreatment and detection methods of TBC and HBCDs were optimized. The samples were freeze-dried, Soxhlet extraction, over-composite silica gel chromatography column, rotary evaporation and nitrogen concentration, and finally were separated and detected by UPLC-MS-MS. In order to ensure the accuracy of the experiment and to carry out the sample recovery experiment, the isotopic labeled [13C12]-伪 -, 尾 -, 纬-HBCD was added to all samples as the internal standard of recovery. The recoveries were 88? The range of relative standard deviation (RSD) is 4.73 / 9.11. The results showed that the detection rate of TBC was 100%, the content was between 0.20-29.03 ng g ~ (-1), the average content was 6.88 ng g ~ (-1); The detectable rates of 伪 -, 尾 -, 纬-HBCD were 75 / 71and 96, respectively. The average content of 伪 -, 尾 -, 纬-HBCD was 0.69 ng / g ~ (-1) 0.42 ng / g ~ (-1) and 5.20 ng / g ~ (-1), respectively. The percentage of 伪 -, 尾 -, 纬-HBCD were 10.1% (5.7-17.0%), 6.1% (3.0-12.1%) and 83.8% (73.2-100.0%), respectively. The average HBCDs content (10.46 ng g ~ (-1) at the Yellow River Estuary is higher than that at the other points, and the TBC and HBCDs contents are lower in the sampling sites along the Yellow River. It is possible that the pollution from the upstream diversion of the Yellow River does not flow through the Yellow River's old road, nor does it deposit with the sediment carried by the runoff, and the government has issued policies to protect the Yellow River's old road. In addition, long distance air transport is one of the ways of TBC,HBCDs transport, but the main pollution is point source pollution. 4. 4. The results were analyzed with SPSS 17.0. (1) the correlation analysis of TBC and HBCDs showed that there was a significant correlation among the three isomers of HBCDs, and there was a weak correlation between the isomers of TBC and HBCDs. These results suggest that there may be some differences between TBC and HBCDs. (2) there is a weak positive correlation between TOC and TBC,HBCDs, and the correlation coefficients of TOC and TBC, 伪-HBCD, 尾-HBCD, 纬-HBCD, 危 HBCDs are: rn 0. 154 (p0. 473), and the correlation coefficient between TOC and TBC, 伪-HBCD, 尾-HBCD, 纬-HBCD, 危 HBCDs is 0. 154 (p0. 473). The results were as follows: (1) 0.138 (p0. 522), 0. 02 (p0. 917), 0. 295 (p0. 162), 0. 275 (p0. 194). The results show that the content of total organic carbon in sediments is one of the factors affecting the distribution of BFRs. (3) the reserves of TBC, 伪 -, 尾 -, 纬-HBCD and 危 HBCDs in sediments of wetlands in the Yellow River Delta are estimated. The exposure pathways of TBC and HBCDs including occupational exposure and non-occupational exposure (diet exposure, inhalation exposure, skin intake, etc.) were analyzed. (4) to further understand the levels of TBC and HBCDs in the sediments of the Yellow River Delta wetland. The results showed that the content of TBC was about 2 times higher than that of Jiaozhou Bay wetland, and the content of HBCDs was slightly lower than that of Jiaozhou Bay wetland. Compared with other parts of the world, the HBCDs content (8.40 ng?g-1) of the wetland in the Yellow River Delta is at the middle level.
【学位授予单位】：青岛大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X592

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