中国科学院生态环境研究中心机构知识库
Advanced  
RCEES OpenIR  > 环境化学与生态毒理学国家重点实验室  > 学位论文
题名: 新型四溴双酚 A/S类污染物的发现 及其环境行为研究
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.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/36892
Appears in Collections:环境化学与生态毒理学国家重点实验室_学位论文

Files in This Item:
File Name/ File Size Content Type Version Access License
刘爱风--新型四溴双酚AS类污染物的发现及其环境行为研究.pdf(5824KB)学位论文--限制开放 联系获取全文

Recommended Citation:
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.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[刘爱风]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[刘爱风]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Copyright © 2007-2017  中国科学院生态环境研究中心 - Feedback
Powered by CSpace