發(fā)布時(shí)間：2018-12-08 16:18

【摘要】：隨著持久性有機(jī)污染物的大量使用,環(huán)境問題變的越來越嚴(yán)重。一些國家和國際組織開始禁止或者限制它們的生產(chǎn)和使用,例如:多溴聯(lián)苯醚(PBDEs)和多氯聯(lián)苯(PCBs)。然而,一些新型的溴代阻燃劑(BFRs)開始出現(xiàn),例如:三(2,3二溴丙基)異氰脲酸酯(TBC)、六溴環(huán)十二烷(HBCDs)、四溴雙酚A(TBBPA),它們被大量應(yīng)用于石油化工業(yè)、機(jī)械制造業(yè)、電子電器產(chǎn)品制造業(yè)中,研究表明它們具有類似于持久性有機(jī)污染物(POPs)的性質(zhì),并廣泛分布于環(huán)境中。本文以黃河三角洲濕地為環(huán)境模型,研究該濕地沉積物中TBC和HBCDs的污染水平、組成特征、與TOC之間相關(guān)性、儲(chǔ)量估計(jì)以及暴露風(fēng)險(xiǎn)等。論文的主要內(nèi)容與結(jié)論如下:1.本實(shí)驗(yàn)優(yōu)化了TBC和HBCDs前處理及分析檢測(cè)方法,對(duì)樣品進(jìn)行冷凍干燥、索氏提取、過復(fù)合硅膠層析柱、旋轉(zhuǎn)蒸發(fā)及氮吹濃縮,最后進(jìn)UPLC-MS-MS分離檢測(cè)。為保證實(shí)驗(yàn)精確度,進(jìn)行樣品加標(biāo)回收實(shí)驗(yàn),所有樣品中均加入同位素標(biāo)記的[13C12]-α-、β-、γ-HBCD作為回收率內(nèi)標(biāo),回收率分別為88 102%、93 107%、83 98%,相對(duì)標(biāo)準(zhǔn)偏差(RSD)的范圍是4.73 9.11%。2.實(shí)驗(yàn)結(jié)果表明:TBC的檢出率為100%,含量在0.20-29.03 ng·g-1之間,平均含量為6.88 ng·g-1;α-、β-、γ-HBCD的檢出率分別為75%、71%、96%,平均含量分別為0.69 ng·g-1、0.42 ng·g-1、5.20 ng·g-1;α-、β-、γ-HBCD所占的比例分別為10.1%(5.7 17.0%)、6.1%(3.0 12.1%)、83.8%(73.2 100.0%)。3.黃河口處采樣點(diǎn)HBCDs平均含量(10.46 ng·g-1)相對(duì)其他點(diǎn)較高,沿黃河故道采樣點(diǎn)TBC和HBCDs的含量較低�？赡苁屈S河改道上游的污染不流經(jīng)黃河故道,也不會(huì)隨著徑流的泥沙攜帶而沉積,并且政府出臺(tái)了保護(hù)黃河故道的政策。另外,空氣進(jìn)行遠(yuǎn)距離傳輸是TBC、HBCDs遷移的方式之一,但主要的污染方式還是點(diǎn)源污染。4.用SPSS 17.0對(duì)檢測(cè)結(jié)果進(jìn)行分析(1)對(duì)TBC和HBCDs進(jìn)行相關(guān)性分析表明:HBCDs三種同分異構(gòu)體之間顯著相關(guān),TBC與HBCDs各同分異構(gòu)體之間存在弱相關(guān),這表明TBC與HBCDs的污染源可能存在一定的區(qū)別。(2)TOC與TBC、HBCDs呈弱的正相關(guān)性,TOC與TBC,α-HBCD,β-HBCD,γ-HBCD,ΣHBCDs含量相關(guān)系數(shù)分別為: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)。這一結(jié)果表明:沉積物中總有機(jī)碳含量是影響B(tài)FRs分布的因素之一。(3)對(duì)黃河三角洲濕地沉積物中TBC、α-、β-、γ-HBCD和ΣHBCDs進(jìn)行儲(chǔ)量估計(jì),并對(duì)TBC和HBCDs的暴露途徑包括職業(yè)暴露和非職業(yè)暴露(飲食暴露、吸吸暴露、皮膚攝入等)進(jìn)行分析。(4)為進(jìn)一步了解黃河三角洲濕地沉積物中TBC和HBCDs的水平,將該區(qū)域與膠州灣濕地進(jìn)行對(duì)比,結(jié)果表明:TBC含量約高于膠州灣濕地2倍,HBCDs的含量稍低于膠州灣濕地。在與世界其它地區(qū)對(duì)比中發(fā)現(xiàn),黃河三角洲濕地HBCDs的含量(8.40 ng?g-1)處于中等水平。
[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]-偽 -, 尾 -, 緯-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 偽 -, 尾 -, 緯-HBCD were 75 / 71and 96, respectively. The average content of 偽 -, 尾 -, 緯-HBCD was 0.69 ng / g ~ (-1) 0.42 ng / g ~ (-1) and 5.20 ng / g ~ (-1), respectively. The percentage of 偽 -, 尾 -, 緯-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, 偽-HBCD, 尾-HBCD, 緯-HBCD, 危 HBCDs are: rn 0. 154 (p0. 473), and the correlation coefficient between TOC and TBC, 偽-HBCD, 尾-HBCD, 緯-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, 偽 -, 尾 -, 緯-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.
【學(xué)位授予單位】：青島大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X592

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