本论文以山东省小清河和黄、东海区域的沉积物和水体为研究对象，以小清河中的多环芳烃、卤代阻燃剂这两种典型有机污染物以及黄、东海区域中卤代阻燃剂为目标物，分析了其浓度水平和空间分布特征，探讨了有机污染物从河流到海洋的迁移输送过程，评估了解小清河和黄、东海有机污染物的污染状况，揭示了洋流作用下河流对海洋污染物的输入所产生的影响。研究结果对该区域污染物的地球化学循环具有重要的科学意义。

河流和海洋环境中的有机污染物可能来自于地表径流物质的输入、人类活动的直接排放、大气沉降和污染物的降解等，另外污染物还可以通过大气的长距离输送和气－水界面交换而进入到海洋。河流是地表水循环的重要组成部分，污染物会随着河流迁移并最终汇入海洋，导致海洋成为一些污染物主要的汇。污染物在进入海洋后引起的海洋环境污染问题是影响我国海洋环境安全的一个重要因素。通过对小清河流域多环芳烃和卤代阻燃剂的研究表明：（1）多环芳烃（PAHs）和卤代阻燃剂（HFRs）在小清河沉积物和水体中分布较广泛，沉积物和水体中的Σ₁₅PAHs浓度范围分别为17.15-3808 ng/g dw（平均浓度为988.7 ng/g dw）、10.40-337.3 ng/L（平均浓度为89.63 ng/L）；沉积物中的ΣHFRs浓度范围为3.663-232.9 ng/g dw。（2）沉积物中多环芳烃的组成主要是以4环和5环为主，水体中的主要以2环和3环为主。沉积物中卤代阻燃剂的组成主要是以十溴二苯乙烷（DBDPE）和十溴联苯醚单体（BDE209）这两种十溴产品为主，水体中DPs和DBDPE这两种物质占主要部分。（3）从小清河源头到河口站位，多环芳烃和卤代阻燃剂这的浓度及分布特征有明显的差异性。对于多环芳烃，河流段沉积物和水体的污染程度高于河口、海湾的样品；而对于卤代阻燃剂，从河口到莱州湾的沉积物卤代阻燃剂浓度普遍较高，这可能是由于潍坊和莱州湾临岸溴系阻燃剂生产地的陆源排放所造成的。河口沉积物中卤代阻燃剂浓度较高可能与河口最大浑浊带的滞留效应有关。点源排放是影响这两种有机污染物浓度及分布特征的主要因素。总之，小清河多环芳烃和卤代阻燃剂这两种污染物的污染程度都处于较严重的水平。

黄海卤代阻燃剂污染程度高于东海的。沉积物中ΣPBDEs和BDE209的浓度范围分别是0.3-108.5 pg/g dw（平均浓度为20.4 pg/g dw）和1.1-924 pg/g dw（平均浓度为127 pg/g dw）；ΣaBFRs和DBDPE的浓度范围分别是n.d.-293 pg/g dw（平均浓度为60.2 pg/g dw）和n.d.-9460 pg/g dw（平均浓度为1700 pg/g dw）。水体中BDE209和DBDPE的浓度范围分别为0.11-35.68 pg/L和n.d.-199.11 pg/L。沉积物卤代阻燃剂分布特征为：沉积区高，沉积区外低；水体中卤代阻燃剂分布特征为：近岸高，远岸较低。这两种环境介质均以DBDPE和BDE209为主要污染物，说明该海域卤代阻燃剂的污染主要源于工业十溴联苯醚的应用和排放，这与我国卤代阻燃剂市场工业品的使用状况一致。我国溴系阻燃剂最大的生产地位于莱州湾附近的潍坊海滨经济开发区，受山东半岛沿岸流的携带，黄河入海泥沙在冬季能穿过莱州湾、渤海海峡，进入黄海，在黄海沉积区沉积。由于水动力条件（受山东半岛沿岸流、黄海沿岸流和黄海暖流形成的气旋式涡旋控制）以及河流物质的输入，黄河泥沙在向黄海传输的过程中吸附莱州湾高浓度的阻燃剂，在渤海沿岸流和黄海沿岸流的作用下，泥沙与阻燃剂共迁移共沉积，最终传输到北黄海和南黄海。

This thesis focuses on the distribution and source of typical organic pollutants in the sediment and water of Xiaoqing River in Shandong Province and Yellow Sea and East China Seas. Polycyclic aromatic hydrocarbons (PAHs) and halogenated flame retardants (HFRs) were investigated in Xiaoqing River, Yellow Sea and East China Sea. Concentrations and spatial distributions were studied to explore the transport process of organic pollutants from river to ocean, to assess the pollution status of this region and to reveal the influence of river inputting of pollutants on sea under the influence of ocean currents.

Organic pollutants in river and marine environment may come from land surface runoff, direct emission of human activities, atmospheric deposition and pollutants degradation. In addition, pollutants can also be imported into the ocean through long range atmospheric transport and air-water exchange. River is an important part of the surface water circulation and pollutants can migrate along rivers and eventually enter the ocean. As a result, the ocean is the main sink of certain pollutants. Marine pollution caused by organic contaminants is a pressing threaten the safety of marine ecosystem. Water and sediment samples were collected from the headwaters to the estuary of the Xiaoqing River to investigate the distribution and fate of PAHs and HFRs. The results show that: (1) PAHs and HFRs were widely distributed in sediments and water of Xiaoqing River. The concentration range of PAHs in sediments and water was 17.15-3808.01 ng/g dw (average: 988.72 ng/g dw) and 10.40-337.31 ng/L (average: 89.63 ng/L), respectively. The concentration of HFRs in sediments ranged from 3 to 232.94 ng/g dw. (2) PAHs were mainly composed of 4, 5 rings in sediments and 2, 3 rings in water. The composition of HFRs in sediments was mainly composed of DBDPE and BDE209. DPs and DBDPE in water were the main components. (3) There was obvious difference in the concentration and distribution characteristics of PAHs and HFRs from the headwaters to estuary of Xiaoqing River. PAHs at the riverine sites were higher than those at the estuarine sites in both sediment and water samples. The concentration of HFRs in sediments from estuary to Laizhou Bay was generally high, which may be due to the land emission from BFR manufacturer in Weifang and Laizhou Bay. Higher concentration of HFRs in estuarine sediments may be related to the scavage effect of estuarine maximum turbidity zone. Point source emission was the main factor affecting the concentration and distribution characteristics of these two classes of organic pollutants. In a word, the pollution of PAHs and HFRs in Xiaoqing River was at a serious level.

The concentration of HFRs in the YS is higher than those in the ECS. The ΣPBDEs and BDE209 concentrations were 0.3-108.5 pg/g dw and 1.1-924 pg/g dw, with mean values of 20.4 and 127 pg/g dw, respectively. The concentrations range of ΣaBFRs and DBDPE were from n.d. to 293 pg/g dw (with a mean of 60.2 pg/g dw) and from n.d. to 9460 pg/g dw (with a mean of 1700 pg/g dw), respectively. The concentration levels of BDE209 and DBDPE in surface water were 0.11-35.68 pg/L and n.d.-199.11 pg/L, respectively. For sediment the level of HFRs was high in the mud zone. From nearshore to offshore, the concentration of HFRs in water showed a slightly decrease trend in the Yellow Sea and East China Sea. The largest BFR manufacturer located in Weifang (Coastal Economic Development Zone). Owing to hydrodynamic conditions (controlled by cyclonic eddy formed by the YS coastal current, the YS warm current and the BS coastal current) and inputting of river materials, the high concentration of HFRs in the YS may originate from the inputting of land-based source near Laizhou Bay. It was speculated that these pollutants would eventually be transported to the North Yellow Sea and the South Yellow Sea under the influence of the Bohai Sea coastal current and the Yellow Sea coastal current.

第1章 绪论............................................... 1

1.1 持久性有机污染物（POPs）简介....................................... 1

1.1.1 卤代阻燃剂简介.................................................. 1

1.1.2 多环芳烃简介.................................................... 8

1.2 国内外研究进展及发展趋势........................................... 9

1.2.1 国内外卤代阻燃剂研究进展........................................ 9

1.3 研究目的、意义和内容.............................................. 12

1.3.1 研究目的和意义................................................. 12

1.3.2 研究内容....................................................... 14

第2章 样品采集与分析.................................... 15

2.1 样品采集.......................................................... 15

2.1.1 研究区域介绍................................................... 15

2.1.2 样品的采集..................................................... 18

2.2 样品的分析........................................................ 19

2.2.1 TOC的测定.................................................... 19

2.2.2 样品的实验分析................................................. 19

2.3 质量保证与质量控制（QA/QC）...................................... 21

第3章 小清河多环芳烃与卤代阻燃剂的分布特征.............. 23

3.1 小清河沉积物和水体中多环芳烃的浓度及空间分布特征.................. 23

3.1.1 沉积物中多环芳烃的污染水平及组成分析........................... 23

3.1.2 水体中多环芳烃的污染水平及组成分析............................. 25

3.1.3 水相和颗粒相中多环芳烃的分配................................... 27

3.1.4 小清河沉积物中多环芳烃的来源分析............................... 28

3.1.5 多环芳烃毒性及潜在生态风险..................................... 29

3.2 小清河沉积物和水体中卤代阻燃剂的浓度及空间分布特征................ 30

3.2.1 沉积物中卤代阻燃剂的污染水平................................... 30

3.2.2 水体中卤代阻燃剂的污染水平..................................... 31

3.2.3 小清河中卤代阻燃剂的分布特征................................... 33

3.3 小结.............................................................. 34

第4章 黄海和东海沉积物中HFRs的分布特征与来源分析....... 35

4.1 黄海和东海PBDEs在沉积物中的浓度及空间分布特征................... 35

4.1.1 PBDEs在沉积物中的污染水平.................................... 35

4.1.2 PBDEs的含量组成分析.......................................... 38

4.2 黄海和东海aBFRs和DPs在沉积物中的浓度及空间分布特征............. 40

4.2.1 aBFRs及DPs分别在黄海和东海沉积物中的污染水平................ 40

4.2.2 aBFRs及DPs在沉积物中的整体污染水平.......................... 42

4.3 卤代阻燃剂与理化系数的相关性分析.................................. 45

4.3.1 HFRs单体之间的相关性分析...................................... 45

4.3.2 与TOC和粒度的相关性分析...................................... 46

4.4 本研究沉积物中BFRs浓度水平与国内外研究对比...................... 48

4.5 黄海和东海区域沉积物中HFRs的空间分布特征及来源分析.............. 50

4.6 本章小结.......................................................... 52

第5章 黄海和东海表层水中HFRs的分布特征................. 54

5.1 黄海和东海表层水中PBDEs的浓度水平、组成及空间分布特征............ 54

5.1.1 黄海和东海表层水中PBDEs的浓度及空间分布特征................... 54

5.1.2 PBDEs在黄海和东海表层水中的单体组成特征...................... 59

5.2 黄海和东海表层水中aBFRs及DPs的浓度水平、组成及空间分布特征..... 60

5.2.1 aBFRs及DPs的浓度及组成...................................... 60

5.2.2 aBFRs及DPs的空间分布特征.................................... 63

5.3 本章小结.......................................................... 63

第6章 结论与展望........................................ 65

6.1 结论.............................................................. 65

6.2 创新与展望........................................................ 66

参考文献................................................. 67

致谢..................................................... 75

作者简历及攻读学位期间发表的学术论文与研究成果........... 77