新型四溴双酚 A/S类污染物的发现 及其环境行为研究
文献类型：学位论文
| 作者 | 刘爱风 |
| 学位类别 | 博士 |
| 答辩日期 | 2016-05 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 北京 |
| 导师 | 江桂斌 ; 史建波 |
| 关键词 | Tetrabromobisphenol A, Tetrabromobisphenol S, Novel brominated contaminants, Environmental behaviors, Orbitrap high resolution mass spectrometry. 四溴双酚 A，四溴双酚 S，新型溴代污染物，环境行为，Orbitrap高分 辨质谱。 |
| 其他题名 | Identification and Environmental Behaviors of Novel Tetrabromobisphenol A/S Derivatives |
| 学位专业 | 环境科学 |
| 中文摘要 | 四溴双酚 A（TBBPA）及其衍生物是目前应用最广泛的溴代阻燃剂（BFR），四溴双酚 S（TBBPS）及其衍生物是 TBBPA的替代型 BFR。目前在多种环境介质中都检测出了高含量的TBBPA/S及其衍生物，如TBBPA bis(allyl ether)（TBBPA-BAE）、TBBPA bis(2,3-dibromopropyl ether)（TBBPA-BDBPE）、TBBPA bis(2-hydroxyethyl ether)（TBBPA-BHEE）和 TBBPS-BDBPE。伴随着 TBBPA/S 衍生物的大量生产和使用，新型 TBBPA/S类似物以副产物和转化产物形式出现在环境中。然而，由于缺乏标准品和分析方法，新型 TBBPA/S类似物的环境来源、分布、归趋和毒性都不明晰。在本论文的研究中，使用自主合成的标准品，建立了高效、灵敏的分析方法，在环境中发现了 8种新型 TBBPA/S类副产物和3种转化产物，它们在环境中分布广泛，成为具有潜在生物富集能力和环境危害的溴代污染物。 通过优化合成方法，在实验室中合成了8种新型TBBPA/S类似物，包括TBBPA mono(allyl ether)（ TBBPA-MAE）、 TBBPA mono(2-bromoallyl ether)（TBBPA-MBAE）、TBBPA mono(2,3-dibromopropyl ether)（TBBPA-MDBPE）、TBBPA mono(2-hydroxyethyl ether)（TBBPA-MHEE）、TBBPA mono(glycidyl ether)（TBBPA-MGE）、TBBPS-MAE、TBBPS-MBAE和 TBBPS-MDBPE，经过核磁共振仪和高分辨质谱进行结构鉴定后，HPLC-UV测定的合成化合物的纯度范围为 96%-99%，此 8种化合物用于后续研究的标准品。 分别建立了高效、灵敏的 HPLC-ESI-MS/MS和 UHPLC-Orbitrap-HRMS方法用于新型 TBBPA/S类污染物的分析，并优化了不同环境样品基质的前处理技术，将液液萃取、加速溶剂提取、固相萃取技术用于环境样品的提取和净化中，针对固体样品，优化后的方法检出限为 0.6-80 pg/g干重（dw）；针对液体样品，优化后的方法检出限为 0.2-1.5 ng/L。两个方法对 TBBPA/S类污染物检测均具有很高的选择性和灵敏度，但 UHPLC-Orbitrap-HRMS方法还能够进行未知污染物的回溯分析，能够更全面的反映样品信息，对未知污染物的鉴定具有许多潜在优势。 使用建立的分析方法首次报道了溴代阻燃剂工厂周围环境和渤海软体动物样品中新型 TBBPA/S类副产物的分布特征。在湖南省的溴代阻燃剂工厂周围采集的沉积物、土壤、稻壳、蚯蚓样品中均检测到了 TBBPA-MAE和 TBBPA-MDBPE，其在沉积物中的浓度最高，浓度范围为 0.7−346.6 ng/g dw，土壤、稻壳和蚯蚓样品浓度水平相当，浓度范围为 0.09-1.0 ng/g dw；TBBPA-MAE和TBBPA-MDBPE在渤海地区采集的软体动物样品中的浓度范围为 ND-1.41 ng/g dw，检出率分别为 41%和 32%。通过分析发现，TBBPA-MAE和 TBBPA-MDBPE是工业品TBBPA-BAE和TBBPA-BDBPE的副产物，工厂是其主要的污染源。TBBPA-MAE和 TBBPA-MDBPE在渤海的软体动物中检出，说明新型的 TBBPA类污染物能够进入动物体内，具有潜在的生物富集能力。TBBPA-MHEE和TBBPA-MGE是工业品 TBBPA-BHEE和溴化环氧树脂的副产物，工业废水和海水中的检出浓度范围为 ND-88.5 ng/L，结果说明 TBBPA-MHEE和 TBBPA-MGE能够伴随工厂排污进入环境中，成为新型的污染物。在山东省寿光市采集到的软体动物样品中检测到 TBBPS-MAE、TBBPS-MBAE和 TBBPS-MDBPE，浓度范围为 ND-4.1 ng/g dw，检出率为5%-95%。结果分析发现TBBPS-MAE、TBBPS-MBAE和TBBPS-MDBPE是工业品TBBPS-BDBPE的副产物，它们已经成为环境中广泛存在的污染物，且其生物富集能力和潜在毒性明显高于 TBBPS-BDBPE。 针对 TBBPA/S及其九种类似物，研究了它们在渤海食物网中的分布特征及营养级传递规律。TBBPA及五种类似物的浓度范围为 ND-2782.8 ng/g脂重（lw）；TBBPS及四种类似物的浓度范围为ND-927.8 ng/glw。TBBPA、TBBPS、TBBPA-MAE、TBBPA-MDBPE、TBBPS-MAE、TBBPS-MBAE和TBBPS-MDBPE的检出率均大于 86%，并且这七种物质的浓度与营养级之间呈现显著的负相关性，其营养级放大因子从 0.31到 0.55，说明这七种污染物在渤海食物网中呈现营养级稀释的趋势。对新型 TBBPA衍生物的环境转化过程进行了研究，鉴定了转化产物，分析了转化产物的环境行为。TBBPA-MDBPE在超还原态的 VB12存在的厌氧条件下，转化为 TBBPA及新型的溴代双酚 A类污染物：TBBPA-MAE、Tribromobisphenol A mono(allyl ether)（TriBBPA-MAE）、dibromobisphenol A mono(allyl ether)（ DBBPA-MAE）、hydroxyl-tribromobisphenol A mono(allyl ether)（HTriBBPA-MAE）、tribromobisphenol A和 ibromobisphenol A。这些新型的溴代污染物在 BFR工厂周围的土壤样品中的浓度范围为ND-5837.0 ng/g dw，检出率范围为 7%-94%，并且 TriBBPA-MAE，DBBPA-MAE和 HTriBBPA-MAE是首次在环境中发现。TBBPA衍生物的广泛应用，尤其是TBBPA-BDBPE，会产生多种结构类似的副产物和降解产物，其进入环境中形成新型的溴代污染物，具有生物富集能力和潜在的环境危害性。TBBPA-MDBPE在 CCAs条件下的厌氧转化产物指导环境污染物的识别，为环境中新型 TBBPA类污染物的发现提供了有效和可行的新方法。 以上研究为评价 TBBPA/S类溴代阻燃剂在我国的环境分布、迁移、转化和生物富集规律提供了方法，开拓了新型TBBPA/S污染物的研究思路，丰富了BFRs相关的研究内容，为综合评价 TBBPA类溴代阻燃剂的环境危害性提供了科学的数据和技术支持。 |
| 英文摘要 | Tetrabromobisphenol A (TBBPA) and its substitute, tetrabromobisphenol S(TBBPS), are two kinds of widely used brominated flame retardants (BFRs). TBBPA,TBBPS and their derivatives, such as TBBPA bis(allyl ether) (TBBPA-BAE), TBBPA bis(2,3-dibromopropyl ether) (TBBPA-BDBPE), TBBPA bis(2-hydroxyethyl ether)(TBBPA-BHEE) and TBBPS bis(2,3-dibromopropyl ether) (TBBPS-BDBPE), have been detected in various environmental matrices. With the production and application of TBBPA/S derivatives, many potential TBBPA/S analogs would emerge in the environment as the byproducts and degradation products. However, due to lacking of pure standards and analytical method, their environmental sources, distribution, fate and toxicity have not been studied. In this work, 8 TBBPA/S byproducts and 3 transformation products were identified in environmental matrices based on synthesized standards and developed analytical methods. The results suggested that the identified TBBPA/S byproducts and degradation products are the novel contaminants with potential bioaccumulative capacities and environmental risks. Eight TBBPA/S analogs, including TBBPA mono(allyl ether) (TBBPA-MAE),TBBPA mono(2-bromoallyl ether)(TBBPA-MBAE),TBBPA mono(2,3-dibromopropyl ether) (TBBPA-MDBPE), TBBPA mono(2-hydroxyethyl ether) (TBBPA-MHEE), TBBPA mono(glycidyl ether) (TBBPA-MGE), TBBPS-MAE、TBBPS-MBAE and TBBPS-MDBPE, were synthesized and characterized by 1HNMR and high resolution mass spectrometry (HRMS). Their purities ranged from 96% to 99%. These 8 synthesized TBBPA analogs were used as the standards for the following studies. The high effective and sensitive methods based on HPLC-ESI-MS/MS and UHPLC-Orbitrap-HRMS were developed after optimization of the pretreatment procedures with liquid-liquid extraction, accelerated solvent extraction and solid phase extraction technique. The method detection limits (MDLs) for solid samples ranged from 0.6 to 80 pg/g dry weight (dw), and the MDLs for water samples ranged from 0.2 to 1.5 ng/L. Both HPLC-ESI-MS/MS and UHPLC-Orbitrap-HRMS methods showed good sensitivity and selectivity, while UHPLC-Orbitrap-HRMS method could screen the sample under the full scan mode and give more sample information along with the quantification of target compounds. The novel TBBPA/S analogs were identified in the environmental samples collected near the BFR factories and mollusk samples collected from the Chinese Bohai Sea for the first time. TBBPA-MAE and TBBPA-MDBPE were detected in soil,sediment, rice hull, and earthworm samples collected near a BFR factory of Hunan Province. The high concentrations were detected in sediment samples ranging from 0.7 to 346.6 ng/g dw; the concentrations in soil, rice hulls and earthworm were at the same level and in range of 0.09−1.0 ng/g dw. The concentrations of TBBPA-MAE and TBBPA-MDBPE in mollusk samples ranged from ND to 1.41 ng/g dw, and the detection frequencies were 41% and 32%, which indicated their bioaccumulative capacities. TBBPA-MAE and TBBPA-MDBPE were confirmed to be the byproducts of commercial TBBPA-BAE and TBBPA-BDBPE, which could be co-produced and leaked into the environment with the production process. TBBPA-MHEE and TBBPA-MGE were identified as the byproducts of commercial TBBPA-BHEE and brominated epoxy resins. They were detected in the waste water and sea water samples in the concentration range of ND-88.5 ng/L, indicating they could occur as emerging contaminants in environment with the discharge of the BFR factories.TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE were identified in mollusk samples collected from the Chinese Bohai Sea, and the concentrations ranged from ND to 4.1 ng/g dw, and the detection frequencies ranged from 5% to 95%, indicating their prevailing in the environment. Meanwhile, TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE were also the byproducts as they were detectable in the commercial TBBPS-BDBPE. The distribution and trophic transfer properties of TBBPA/S and nine analogs in the Chinese Bohai Sea food web were studied using an effective method developed for simultaneous analysis of these 11 compounds. The concentrations of TBBPA and five analogs ranged from ND to 2782.8 ng/g lipid weight (lw); for TBBPS and four analogs ranged from ND to 927.8 ng/g lw. The detection frequencies of TBBPA,TBBPS, TBBPA-MAE, TBBPA-MDBPE, TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE were all higher than 86%. The significantly negative correlations between trophic levels and concentrations of TBBPA/S and these five analogs were observed and their trophic magnification factors ranged from 0.31 to 0.55. These results indicated TBBPA/S and byproducts displayed trophic dilution tendencies in the food web of the Chinese Bohai Sea.Meanwhile, we conducted the environmental transformation study of novel TBBPA derivatives, identified the transformation products and analyzed their environmental distribution. The anaerobic transformation of TBBPA-MDBPE generated TBBPA and six novel TBBPA analogs under super-reduced vitamin B12 (CCAs) condition, including TBBPA-MAE, Tribromobisphenol A mono(allyl ether)(TriBBPA-MAE),dibromobisphenol A mono(allyl ether)(DBBPA-MAE),(HTriBBPA-MAE), hydroxyl-tribromobisphenol A mono(allyl ether)Tribromobisphenol A and dibromobisphenol A. Their concentrations ranged from ND to 5837.0 ng/g dw and detection frequencies ranged from 7% to 94%. TriBBPA-MAE,DBBPA-MAE and HTriBBPA-MAE were detected in the environment for the first time. The wide use of TBBPA derivatives, especially TBBPA-BDBPE, have arose severe environmental risk by generating more toxic and bioaccumulative byproducts and degradation products. The transformation of TBBPA-MDBPE with CCAs is an effective and instructive approach for the identification of novel contaminants and the risk assessment of TBBPA and its derivatives. In this dissertation，the environmental distribution, transportation, transformation and bioaccumulation of TBBPA/S and their novel derivatives were well studied based on developed accurate and sensitive methods. The synthesized byproducts combined with the environmental analysis gave new insight into the environmental contaminants identification. The results of this dissertation will supplement the information for the novel BFRs and provide scientific basis for comprehensive evaluation of the environmental and health risks of TBBPA related BFRs. |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/36892]  |
| 专题 | 生态环境研究中心_环境化学与生态毒理学国家重点实验室 |
| 推荐引用方式 GB/T 7714 | 刘爱风. 新型四溴双酚 A/S类污染物的发现 及其环境行为研究[D]. 北京. 中国科学院研究生院. 2016. |
入库方式： OAI收割
来源：生态环境研究中心
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