环渤海主要入海河流有机磷酸酯阻燃剂的初步研究

	环渤海主要入海河流有机磷酸酯阻燃剂的初步研究
	王润梅 1,2
学位类型	硕士
导师	唐建辉
	2015-05-17
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	环境工程
关键词	有机磷酸酯阻燃剂环渤海地区河流沉积物
摘要	为降低人类生活环境的燃烧风险，阻燃剂被广泛应用于建筑材料、汽车、船舶、航空、火车、电子产品、塑料制品、家装饰品和纺织品中。有机磷酸酯（OPEs）是一类重要的有机磷阻燃剂，其阻燃效果好、生产成本低以及生产工艺简单。近年来，溴系阻燃剂由于环境问题在全球范围内逐步禁用，有机磷酸酯阻燃剂作为其主要替代品，生产和使用都有较大程度的增长，但其引起的环境问题也逐渐引起了环境科学工作者的关注，有机磷酸酯阻燃剂已成为新型有机污染物研究的一个新热点。作为潜在持久性有机污染物，当前的研究已证明多种有机磷酸酯具有不同的生物毒性；多种有机磷酸酯尤其氯代烷基磷酸酯在自然环境中难降解；有机磷酸酯可通过吸附在颗粒物上进行中尺度和大尺度迁移。我国目前对有机磷酸酯阻燃剂的研究主要集中在新型有机磷阻燃剂的合成和性能优化等方面，关于其在不同环境介质中的分布及污染状况鲜有报道。我国环渤海地区经济发展速度快，人口密度高，众多的河流对人类生产生活影响重大。河流在人为污染物从陆地向海洋输送过程中扮演着重要的角色，渤海是我国唯一的半封闭内海，入海河流是其重要的污染来源。本论文研究了环渤海地区40条河流有机磷酸酯阻燃剂的分布特征和入海通量。利用液液萃取技术（LLE）和索氏抽提固相萃取技术（SE）结合气相色谱质谱联用仪（GC-MS）建立了河流水样和沉积物样品中有机磷酸酯阻燃剂的分析方法，该方法回收率、线性范围和检测限均较好。利用该方法对我国环渤海地区40条主要河流中有机磷酸酯阻燃剂进行了测定，结果显示所有研究河流水相和沉积物中有机磷酸酯均有检出，各种有机磷酸酯化合物的广泛分布且浓度范围变化较大。水相中12种有机磷酸酯总浓度（∑₁₂OPEs）范围在10—1549 ng/L，平均浓度为300 ng/L。磷酸三（2-氯丙基）酯（TCPP）、磷酸三（2-氯乙基）酯（TCEP）和三苯基氧磷（TPPO）是主要污染物，平均浓度分别为186 ng/L，80 ng/L和224 ng/L。TPPO的污染，尤其是鸭绿江（5852 ng/L）和界河（1283 ng/L），值得注意。沉积物中8种有机磷酸酯总浓度（∑₈OPEs）范围在TCEP>TDCPP。 40条河流输送OPEs的通量为16.0±3.2 吨/年，输送TPPO通量为113±22.6吨/年。输送到辽东湾（7.0±1.4 吨/年）有机磷阻燃剂总量比输送到渤海湾（3.4±0.7 吨/年）和莱州湾（1.5±0.3吨/年）的高。研究发现环渤海地区有机磷酸酯阻燃剂的“源”具有相似性，各河流有机磷阻燃剂分布模式相似。沉积物中总有机碳（TOC）、总氮（TN）、总有机碳和总氮的碳氮元素比（C_org/N_total）、粒度和粒径组分（粘土、粉砂和砂）与有机磷酸酯的浓度相关性较弱，不同河流OPE含量和组成差异可能比这些因素对OPE的环境分布和组成的影响更大。有机磷酸酯的log K_OW是其在沉积物和水相中分配的重要控制因素，log K_OW越小的有机磷酸酯越倾向于分配在水相，log K_OW越大的有机磷酸酯越倾向于吸附到悬浮颗粒。水相是有机磷阻燃剂重要的输入途径，水相中有机磷阻燃剂之间较高的相关性是其在水相中分配的结果。本文对我们了解我国地表水有机磷酸酯阻燃剂污染水平提供了依据，为中国水体环境中有机磷酸酯的研究提供了参考依据，为有机磷酸酯的环境风险评价提供了基础数据。我国地表水污染已成为影响我国水安全最突出的因素，在传统污染化学需氧量、氨氮和富营养化等还未改善的同时有机污染如有机磷阻燃剂也必须引起重视。
其他摘要	Flame retardants have been reducing the risk of fires in everyday products such as buildings, cars, ships, airplanes, trains, electronics, plastics, furniture and clothes. Organophosphate esters (OPEs) are important organophosphorus flame retardants with good flame retardant effect, low production cost and uncomplicated production process. Since brominated flame-retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) have gradually been restricted worldwide due to environmental concerns, OPEs, have increasingly been used as alternatives to BFRs in many industrial applications and household products. While the environmental problems caused by OPEs has gradully attracted attention of scientific community, OPEs has become a new hot spot of the research of emerging organic pollutants. As potential persistent organic pollutants, many studies have demonstrated that a few of OPEs are biological toxic, and a few OPEs especially chlorinated alkyl phosphate esters are recalcitrant in natural environment and OPEs may go on mediun and large scale migration by absorbed on particles. Researches in China were mostly focused on the synthesis and performance optimization of OPEs. However, few literatures on concentraion levels and distributions have been reported. The river basins in the study area have been subjected to heavy anthropogenic influences owing to the high-speed development of the agriculture, industry and overall economy. Rivers are one of the major sources/pathways for terrestrial pollutants into the sea. The Bohai Sea is a semi-enclosed Chinese water body, and these rivers are the major sources for pollutants to the Bohai Sea. This study focused on the occurrence and spatial distribution of OPEs in 40 major rivers entering into the Bohai and Yellow Seas and the riverine input of OPEs was estimated. In this study, analytical methods based on Soxhlet Extraction liquid-liquid extration and soxhlet extraction coupled to gas chromatograph-mass spectrometer (GC-MS) were established for determination of OPEs in river water and sediment samples. High quality QA/QC data were obtained. OPEs were determined in water samples from 40 rivers and in sediment samples from 35 rivers. The results showed that the detection rates of OPEs in aqueous phase and sediment were 100% and OPEs were widely distributed and in a wide range. Total OPEs (∑₁₂OPEs) in aqueous phase ranged from 10 to 1549 ng/L, with an average of 300 ng/L. The most common OPEs detected in river water were TCPP, TCEP and TPPO, at mean concentrations of 186 ng/L, 80 ng/L and 224 ng/L, respectively. Priority attention should be given to TPPO contamination in rivers around the Bohai Sea, especially in the Yalu (5852 ng/L) and Jiehe (1283 ng/L) Rivers. Total OPEs (∑₈OPEs) in sediment particle phase ranged from TCEP>TDCPP. According to the sample concentrations and annual runoff, the total riverine input of OPEs was estimated to be 16.0±3.2 t/yr and the total riverine input of TPPO was estimated to be 113±22.6 t/yr . Liaodong Bay received relatively high riverine input of 12 organophosphorus compounds (7.0±1.4 t t/yr) in comparison to Bohai Bay (3.4±0.7 t/yr) and Laizhou Bay (1.5 ± 0.3 t/yr). The study found that the sources of OPEs from the Bohai area were similar and their distribution patterns in aqueous phase were similar. TOC, TN, C_org/N_total, sediment particle size and particle size fractions (clay, silt and sand) didn’t influence the concentration of OPEs in sediment. Log K_OWvalue of OPEs was an improtant factor contrlling the OPEs distribution in particle phase and aqueous phase. The lower the log K_OWvalue was, the more likely OPEs was inclined to distribute in aqueous phase. The greater the log K_OWvalue was, the more likely OPEs was inclined to distribute in particle phase. The aqueous phase was an important input way for OPEs and allocating in the aqueous phase resulted to the good correlations between OPEs. This paper helped to understand the pollution situation and regional distribution of OPEs in Chinese surface water, to lay the groundwork for OPEs study in water body, to provide reference data for environmental risk assessment of OPEs. Surface water pollution has become the most prominent factor affecting water security in China. Attention should be given to traditional pollutants such as COD, ammonia and nitrogen pollution and eutrophication as well as organic pollutants such as OPEs.
语种	中文
文献类型	学位论文
条目标识符	http://ir.yic.ac.cn/handle/133337/7921
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	1.中国科学院大学 2.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
推荐引用方式 GB/T 7714	王润梅. 环渤海主要入海河流有机磷酸酯阻燃剂的初步研究[D]. 北京. 中国科学院大学,2015.

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