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典型卤代阻燃剂及其衍生物在极地生态系统中的赋存与生物富集
Alternative TitleOccurence and bioaccumulation of typical halogenated flame retardants and related compounds in Arctic and Antarctic regions
孙慧中
Subtype博士
Thesis Advisor张庆华
2018-06
Degree Grantor中国科学院生态环境研究中心
Place of Conferral北京
Degree Name理学博士
Degree Discipline环境科学
Keyword极地,多溴二苯醚,甲氧基和羟基多溴二苯醚,得克隆,生物富集 Polar Region,Polybrominated Diphenyl Ethers,Methoxylated And Hydroxylated Polybrominated Diphenyl Ethers,Dechlorane Plus,Bioaccumulation
Abstract

     卤代阻燃剂因其优异的阻燃性能被广泛应用于工业生产和日用品中。作为添加型阻燃剂,卤代阻燃剂在添加产品的生产、使用和处置过程中通过挥发、渗出等方式释放出来,并对周边环境产生影响。本文以两种主要的卤代阻燃剂——多溴二苯醚(PBDEs)和得克隆(DP)——及其相关化合物甲氧基多溴二苯醚(MeO-PBDEs)、羟基多溴二苯醚(OH-PBDEs)、DP类似物(Dechlorane 602, Dechlorane 603, Dechlorane 604, anti-Cl10-DP, anti-Cl11-DP)为研究对象,分析其在南北极地区陆地和海洋环境中的浓度水平、同类物分布特征及生物富集、放大效应。

        本研究优化了不同环境样品的前处理流程,并建立了气相色谱—三重四级杆质谱法分析极地样品中40种目标污染物(7种PBDEs、13种MeO-PBDEs、13种OH-PBDEs,以及7种DP及相关化合物即Decs)的仪器分析方法。样品经干燥、研磨后先后用正己烷/二氯甲烷和正己烷/甲基叔丁基醚的混合溶剂进行加速溶剂萃取。萃取液先经碱洗,将中性和弱极性组分(PBDEs、MeO-PBDEs和Decs)与极性组分(OH-PBDEs)分离。中性和弱极性组分经复合硅胶柱净化后浓缩,进行仪器分析。极性组分通过酸洗还原后,先用三甲基硅烷基重氮甲烷进性衍生化,再经复合硅胶柱净化后浓缩,进行仪器分析。以同位素内标法(PBDEs、MeO-PBDEs、OH-PBDEs)和内标法(Decs),采用相对响应因子法对目标物进行定量。本方法的标准曲线(线性范围:0.1~200 ng mL-1)响应因子的相对标准偏差(RSD)<25%。在对实际样品的测定时也显示出良好的分析效果。

       本文分析了北极黄河站周边及朗伊尔城附近多种环境介质中目标污染物的浓度水平、同类物组成、生物富集效应和营养级放大作用。北极陆地环境中∑Decs的浓度最高(15.4~18630 pg g-1 干重,dw),其次为∑MeO-PBDEs和∑OH-PBDEs(未检出~794 pg g-1 dw和3.14~1131 pg g-1 dw),∑PBDEs(5.57~270 pg g-1 dw)的浓度最低。海洋生物样品中四种污染物的浓度相当(未检出~59.2 ng g-1 脂重,lw)。北极植物对PBDEs和DPs均具有较强的生物富集作用,而对MeO-PBDEs和OH-PBDEs的富集能力存在物种间差异。对污染物在海洋食物网中营养级放大趋势的研究结果表明,仅部分MeO-PBDEs同类物和∑MeO-PBDEs存在营养级放大,PBDEs、OH-PBDEs和Decs均呈现营养级稀释的趋势。

     南极长城站周边陆地环境样品和沉积物中∑PBDEs和∑Decs的浓度范围为2.33~32.7 pg g-1 dw和未检出~234 pg g-1 dw,而∑OH-PBDEs和∑MeO-PBDEs的浓度高达37.5~26412 pg g-1 dw和8.5~5050 pg g-1 dw。海洋生物样品中四种污染物的水平大致相当,分别为0.06~31.3 ng g-1 lw(∑PBDEs)、0.08~5.84 ng g-1 lw(∑MeO-PBDEs)、0.17~37.8 ng g-1 lw(∑OH-PBDEs)和未检出~19.3 ng g-1 lw(∑Decs)。生物富集因子的计算结果显示DPs和PBDEs在南极植物样品及海洋生物样品均呈现出较强的生物富集作用,而MeO-PBDEs和OH-PBDEs的富集能力存在物种差异。BDE-154和∑MeO-PBDEs在南极海洋食物网中呈现出显著的营养级放大作用,OH-PBDEs和Decs的浓度则呈现出随营养级稀释的规律。

Other Abstract

     Halogenated flame retardants, as one group of additive flame retardants, have been widely applied to industrial and household products. Additive flame retardants may release into environment during production, application as well as recycling process of the products containing flame-retardants. In this study, polybrominated diphenyl ether (PBDEs) and their hydroxylated and methoxylated analogues (OH-PBDEs and MeO-PBDEs), Dechlorane Plus (DP) and the related compounds (Dechlorane 602, Dechlorane 603, Dechlorane 604, anti-Cl10-DP, anti-Cl11-DP) were chosen to investigate their concentration levels, congener distribution, bioaccumulation and trophic magnification in the Arctic and Antarctic region.

         In this paper, the clean-up processes were optimized for analysis target contaminants simultaneously. Meanwhile, the instrumental methods were developed on a gas chromatograph coupled to a triple quadrupole mass spectrometer (GC-MS/MS) for 40 target contaminants. Samples were extracted twice by the accelerated solvent extraction device with n-hexane/DCM and n-hexane/MTBE. The neutral/weak polar components (PBDEs, MeO-PBDEs, DP and the related compounds) and the medium polar ones (OH-PBDEs) were separated by alkaline solution. The former fractions were purified by multilayer silica gel column and concentrated before instrumental analysis. The acid solution were added to the OH-PBDEs fraction for reduction. OH-PBDEs were derivatized by TMSDM, purified by multilayer silica gel column and concentrated before instrumental analysis. 13C-labelled isotope standards and internal standards were used in this method. The method demonstrated a wide linear response of calibration curve ranges from 0.1 to 200 (1-1000) ng mL-1 with the average of relative response factor (RRF) less than 25%. The good sensitivities meet the demands of real sample analysis.     

         Concentration levels, congener distribution, bioaccumulation and trophic magnification of target pollutants in environmental samples from the Arctic Yellow River Station and Longyearbyne City were investigated. The highest concentrations were found for ∑Decs (sum of DP and related compounds, 15.4-18630 pg g-1 dry weight, dw), following by ∑OH-PBDEs (3.14-1131 pg g-1 dw) and ∑MeO-PBDEs (not detected to 794 pg g-1 dw), ∑PBDEs (5.57-270 pg g-1 dw) were at the lowest levels. The concentrations of target pollutants in marine organism were at the similar levels (ranging from not detected to 59.2 ng g-1 lipid equivalent weight, lw). Variations in bioaccumulation capacities of MeO-PBDEs and OH-PBDEs were found for different plant species, while significant bioaccumulation of PBDEs and DP were observed in all six-plant species. Trophic magnification trend was found for MeO-PBDEs. However, trophic dilution trends were observed for PBDEs, OH-PBDEs, DP and related compounds.

         The levels of ∑PBDEs and ∑Decs in terrestrial environmental samples and sediment collected from the Antarctic Great Wall Station and surrounding area were in the range of 2.33 to 32.7 pg g-1 dw and not detected to 234 pg g-1 dw. However, the concentration of ∑OH-PBDEs (37.5-26412 pg g-1 dw) and ∑MeO-PBDEs (8.5-5050 pg g-1 dw) were much higher. The range of target pollutants concentrations in marine organism were 0.06-31.3 ng g-1 lw (for ∑PBDEs), 0.08-5.84 ng g-1 lw (for ∑MeO-PBDEs), 0.17-37.8 ng g-1 lw (for ∑OH-PBDEs) and not detected to 19.3 ng g-1 lw (for ∑Decs). DPs showed the higher bioaccumulation factors (BAFs), while the BAFs of the other pollutants were varied with different plant and marine organism. The trophic transfer of BDE-154 and ∑MeO-PBDEs were observed in marine food web. The low trophic magnification factor values of ∑OH-PBDEs and ∑Decs indicating the trophic dilution trends of these pollutants.

Language中文
Document Type学位论文
Identifierhttp://ir.rcees.ac.cn/handle/311016/41525
Collection环境化学与生态毒理学国家重点实验室
Recommended Citation
GB/T 7714
孙慧中. 典型卤代阻燃剂及其衍生物在极地生态系统中的赋存与生物富集[D]. 北京. 中国科学院生态环境研究中心,2018.
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