环渤海区域表层沉积物中卤代阻燃剂的分布特征及来源研究
甄小妹
学位类型硕士
导师唐建辉
2016-05-22
学位授予单位中国科学院大学
学位授予地点北京
学位专业环境科学
关键词卤代阻燃剂 Hfrs 黄海 渤海 入海河流
摘要 卤代阻燃剂(HFRs)可以增加材料的阻燃性能,因而广泛用于我们生活和生产中。由于使用量的不断增加,HFRs在各种环境介质被广泛检出。HFRs本身带来的环境污染问题是相当严重,某些溴代阻燃剂(BFRs)已经被证明具有POPs毒性,因而在国内外广泛被限制和替代。环渤海地区在我国海洋经济上占据着重要的地位,且拥有较多人口和发达的工业城市,每年有大量的工业废水、生活废水和市政废水直接或者间接(经河流)排放到海洋中去。另外,渤海的莱州湾是我国北方最大的BFRs生产基地,但是目前对于北方海洋环境中aBFRs的研究鲜有报道。
本文分别对黄海四个海湾51个表层沉积物及胶州湾3个入海河流表层沉积物中17种BFRs和渤海108个海洋表层沉积物及35条入海河口表层沉积物中的19种HFRs进行了气相色谱-质谱(GC-MS)分析,研究其含量、组成及分布特征并初步分析其污染物的可能来源。研究结果为:
1)黄海区域大连湾,四十里湾,套子湾,胶州湾及胶州湾的入海河流表层沉积物中9种多溴联苯醚(PBDEs)和8种aBFRs的检测结果为:DBDPE和BDE209是检出率和含量最高的两种BFRs,河流和海湾样品中DBDPE的含量范围分别为130-49940 pg/g dw和160-396 50 pg/g dw,BDE209的含量范围分别为50.0-7820 pg/g dw和nd-10180 pg/g dw,DBDPE的污染程度已经超过了传统的BDE209。所有样品中∑PBDEs(不包括BDE209)的浓度比较低,对于剩余的aBFRs,TBE,TBB和TBPH在海湾沉积物中都没有检出,∑aBFR4(PBT+PBEB+DPTE+HBB)在所有沉积物中的检出的浓度较低。根据DBDPE和BDE209在黄海胶州湾和大连湾的空间分布特征可以发现,污水口上游的含量高于下游海区,他们在河口的含量高于河口下游海区,因此,污水口和河流的排放可能分别是大连湾和胶州湾DBDPE和BDE209的主要来源。另外,四十里湾和套子湾的DBDPE和BDE209的污染可能在受到山东半岛沿岸流的影响下,将生产源区莱州湾附近的BFRs输送到这里并沉积下来。低含量的∑PBDEs和∑aBFR4可能来自于多种因素共同作用,包括含溴产品的沿岸流输送、大气沉降、以及高溴代的PBDEs的降解。
2)渤海及35条入海河流表层沉积物中DBDPE,BDE209,∑PBDEs,∑aBFR7和DPs的检出率均超过69.0%,说明HFRs在渤海区域的广泛存在。DBDPE和BDE209为主要的两种BFRs污染物,这与黄海海湾中研究的结果一致。渤海样品中DBDPE, BDE209,∑PBDEs,∑aBFR7和DPs的均值浓度分别为2560 pg/g dw,250 pg/g dw,16.6 pg/g dw,33.4 pg/g dw和19.7 pg/g dw。本文把渤海分成大连湾,渤海湾,莱州湾,渤海中部和渤海海峡5个部分。渤海入海河流中对应物质的检出率和含量都要比海洋中高,河流样品中主要的两种污染物,DBDPE和BDE209的最高浓度出现在靠近BFRs生产源区的弥河。所有样品中DBDPE与BDE209的含量相关性较好,可能是因为DBDPE是BDE209的替代物,因此具有同源性。HFRs的空间分布特征来分析,可以看出,DBDPE与BDE209污染程度较高的海域,其对应区域的入海河流的该污染物的污染程度也较高。DBDPE和BDE209在辽东湾和渤海湾入海河口的浓度不高,渤海湾和辽东湾污染程度也较低,说明河流输入是渤海DBDPE与BDE209的重要来源。HFRs与TOC和MD相关性分析结果表明,海洋中DBDPE和BDE209分别与TOC及MD的相关性较好,而河流中则没有相关性,渤海和河流样品中∑PBDEs,∑aBFR7和DPs分别与TOC和MD的相关性呈较差或者没有相关性,所以河流中HFRs可能来源于周边的点源和非点源排放,更加证明了河流输入是渤海中DBDPE和BDE209 的主要来源。DPs在渤海的高值区与入海河流的高值区不太一致,说明了河流可能不是DPs的主要来源。低含量的∑PBDEs,∑aBFR7和DPs来源可能是受到多种因素的共同作用。
其他摘要 Halogenated flame retardants (HFRs) are used extensively in domestic and industrial products as addictives to prevent fire. HFRs are detected in various environmental media because of the widespread use. Meanwhile, the residues of HFRs in the environmental media may cause severe environmental and ecological risks as some BFRs have been listed as persistent organic pollutants. Hence, the bans and restrictions of some BFRs have been implemented around the world. The Yellow Sea and Bohai Sea are two important shelf seas which sustain China’s marine economy and coastal urbanization and industrialization. Meanwhile, they are suffering heavily pollution and eutrophication due to the large amount of industrial, domestic, and municipal waste water together with nutrients and pollutants from air deposition pouring in them. Besides, the Laizhou Bay area around Bohai Sea is the largest manufacturing base for BFRs in northern China. However, studies of aBFRs in this region are scarce.
In this study, seventeen BFRs were investigated in 51 marine surface sediment samples and 3 river surface sediment samples from the Yellow Sea and nineteen HFRs were determinate in 108 marine surface sediment samples and 35 riverine surface sediment samples from rivers empting into the Bohai Sea and northern Yellow Sea. All the samples were analyzed by gas chromatography-mass spectrometry (GC-MS). The results of this paper are shown as follows:
1) Nine PBDEs and eight aBFRs were detected in four bays (Dalian Bay, Sishili Bay, Taozi Bay, Jiaozhou Bay, and two rivers discharging into Jiaohzou Bay) of Yellow Sea. DBDPE and BDE209 are two dominant BFRs with the highest detection frequencies and concentrations. The concentrations of DBDPE were ranged from 130 to 49940 pg/g dw and 160 to 39650 pg/g dw in river and marine samples, respectively, and have exceeded those of BDE209 (50.0 to 7820 pg/g dw and nd to 1020 pg/g dw in river and marine samples, respectively) in the four bay areas. The concentrations of DBDPE and BDE209 are higher in the sites around the sewage outlets and river estuaries than other stations, and thus WWTPs and river might be the sources of Dalian Bay and Jiaozhou Bay. Furthermore, transport from Laizhou Bay around the BFR manufacturing base by coastal currents is the major source of BFRs in Taozi Bay and Sishili Bay. TBE, TBB and TBPH are not detected in bay sediments, whereas ∑PBDEs and ∑aBFR4 are detected at low concentrations in all sediments. They are probably attributable to a combination of factors such as low regional usage of these products, atmospheric deposition, coastal currents transportation, and degradation processes for higher BDE congeners.
2) The detection of DBDPE, BDE209, ∑PBDEs , ∑aBFR4 and DPs in the sediments of the Bohai Sea are all more than 69.0%, which means that HFRs are widely existed in this area. DBDPE and BDE209 are both the main HFRs in the rivers and marine sediments from the Bohai Sea, which is consisted with those in the bays of the Yellow Sea. Mean concentrations of DBDPE, BDE209, ∑PBDEs, ∑aBFR7 and DPs in marine samples are 2560 pg/g dw, 250 pg/g dw, 16.6 pg/g dw, 33.4 pg/g dw and 19.7 pg/g dw, respectively. This paper divided Bohai Sea into 5 parts, including the Dalian Bay, the Bohai Sea, the Laizhou Bay, the Central Bohai Sea and the Bohai Strait. The detection frequencies and concentrations of HFRs in rivers (around the Bohai Sea) are higher than those in marine samples, and the highest concentrations of DBDPE and BDE209 are found in the Mi river which is closed to the BFRs manufacturing area. High levels of DBDPE and BDE209 have been found both in the riverine and marine sediment samples of Laizhou Bay. This indicates that BFRs factories influence the concentrations of BFRs in marine and rivers samples. However, DBDPE and BDE209 are both at low concentrations in the Bohai Bay and Dalian Bay, as well as low concentrations of those two BFRs are determined in rivers around this bay. These results show that rivers are the significant source of DBDPE and BDE209. The good correlation between DBDPE and BDE209 indicates that these two BFRs shares common sources. Good correlations between DBDPE with TOC and MD in marine are found, but poor correlations were found in rivers, which is the same for BDE209. Meanwhile, poor correlations were found between TOC and MD with the other HFRs in all sediments. These results show that HFRs of rivers are ascribed to the input of point source or no-point source. The distributions of DPs are contrary to those of DBDPE, so the source of DPs may not be from rivers. The major sources of ∑PBDEs, ∑aBFR7 and DPs are probably attributable to a combination of factors.
文献类型学位论文
条目标识符http://ir.yic.ac.cn/handle/133337/13829
专题中国科学院烟台海岸带研究所知识产出_学位论文
作者单位中国科学院烟台海岸带研究所
第一作者单位中国科学院烟台海岸带研究所
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甄小妹. 环渤海区域表层沉积物中卤代阻燃剂的分布特征及来源研究[D]. 北京. 中国科学院大学,2016.
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