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题名: 环状全氟化合物与氯代多氟醚磺酸在典型区域的环境行为及人体暴露
作者: 王媛1
学位类别: 博士
答辩日期: 2017-05
授予单位: 中国科学院大学
授予地点: 北京
导师: 蔡亚岐
关键词: 环状全氟化合物,氯代多氟醚磺酸,环境行为,生物累积,人体暴露 ; cyclic PFASs, Cl-PFESAs, environmental behavior, bioaccumulation, human exposure
其他题名: Environmental Behavior and Human Exposure of Cyclic Per- and Polyfluorinated alkyl Substances and Cl-PFESAs
学位专业: 环境科学
中文摘要: 全氟和多氟化合物(Per- and polyfluoroalkyl substances,PFASs)的环境问 题一直是近几年的研究热点。它们在环境中广泛存在且不易被降解,并可对生物 和人体造成不良影响。因此,目前许多替代产品被大量生产和使用。这些替代产 品主要包括一些短链的 PFASs和结构中引入醚键和/或氯等杂原子的 PFASs;另 外,虽然一些 PFASs被大量生产和使用多年,但分析技术和科学研究的局限使 得它们一直未曾进入环境科学家的研究视野,近年来色谱质谱技术特别是高分辩 质谱的飞速发展和环境科学研究的不断深入使得它们的环境存在逐渐得以揭示。 我们将上述全氟和多氟化合物统称为新型 PFASs。目前环境科学界对新型 PFASs 的环境行为、生物富集和人体暴露的研究十分有限。本论文以环状 PFASs及其 异构体和氯代多氟醚磺酸(Cl-PFESAs)等新型 PFASs为对象,在建立起定性和 定量分析方法的基础上,研究它们在典型区域中的环境行为及人体暴露,论文主 要包括以下内容: 1、在目前常见 PFASs分析方法的基础上,综合优化常见 PFASs的样品前处 理、色谱分离和质谱检测方法,并对它们的异构体给予了高度关注,完善建立了 包括 Cl-PFESAs在内的多种 PFASs同时分析的方法,方法的检出限和加标回收 率等参数均满足要求,适用于环境水样、底泥和生物组织等实际样品的分析。 2、开展了北京首都机场周边环境中环状 PFASs及其异构体的识别分析、环 境行为和器官特异性的生物累积研究。利用高分辨的四级杆线性离子阱静电场轨 道阱质谱(Orbitrap MS)首次在环境和生物样品中识别分析了全氟乙基环己烷磺 酸(PFECHS)和全氟丙基环戊烷磺酸(PFPCPeS)的五种异构体的存在。地表 水和底泥中环状 PFASs的总浓度分别为 1.04 - 324 ng/L和 0.194,p < 0.01);与常见 PFASs相似,男性 C8 Cl-PFESA的浓度(n = 210;3.25 ng/g,0.08 - 24.34 ng/g)显著高于女性(n = 229;2.88 ng/g,0.04 - 42.72 ng/g;p < 0.05);青年女性体内常见 PFASs和 C8 Cl-PFESA的浓度最低。此外, 通过食鱼的摄入可能是石家庄普通人群 Cl-PFESAs暴露的主要途径。 5、探讨了头发、指甲和尿液作为非侵入性生物监测介质对一些常见和新型 PFASs内暴露指示的有效性和可行性。结果表明,对受高浓度 PFASs暴露影响 的成对血清与指甲样品(n = 8)的分析发现 PFUnDA、PFHxS、PFOS和 C8 Cl-PFESA等发生了具有明显剂量依赖性的从血清到指甲的转移(ρ > 0.74,p < 0.05);实际环境条件下的被动吸收模拟实验表明,56天的暴露仍未发现头发中 有 PFASs的明显吸收,说明可以基本排除实际空气环境直接暴露对头发和指甲 作为内暴露指示者的影响;综合分析PFOS和C8 Cl-PFESA在高低暴露人群血液、 尿液、头发和指甲中的浓度比值和转移关系,发现头发和指甲中 PFOS和 C8 Cl-PFESA浓度水平和人体内暴露存在可能的联系。另外,尿液样品可为血清样 品中无法检测到的短链 PFASs的内暴露提供证据。
英文摘要: In recent years, a growing concern is of the environmental problem on per- and polyfluoroalkyl substances (PFASs) due to their omnipresence, persistence and bioaccumulation. Thus, a large number of substitute compounds have been widely produced and used, which is collectively named emerging PFASs. They mainly include PFASs with shorter-chain carbon or ether bonds added in the perfluoroalkyl chain. However, limited studies reported environmental behavior, bioaccumulation and human health effects of emerging PFASs. Here, we develop the analytical methods for determination of two typical emegering PFASs, cyclic PFASs and Cl-PFESAs, and investigate their environmental behavior, potential impacts on biota and human. The main contents of this dissertation comprise the following five sections: Firstly, on the basis of the established analytical methods for legacy PFASs, the pretreatment and HPLC-MS method were optimized and established for determining cyclic PFASs isomers and Cl-PFESAs in various matrixes. The methods, with good recoveries and repeatability, are appropriate for the detection of PFASs in real samples. Secondly, identification, tissue distribution and bioaccumulation potential of cyclic perfluorinated sulfonic acids isomers in Beijing international airport were studied. Here, we investigated the presence of perfluoroethylenecyclohexane sulfonate (PFECHS) isomers in environmental samples for the first time using a combination of high resolution and tandem mass spectrometry (Orbitrap MS Fusion). Five distinct peaks attributed to different isomers of PFECHS and perfluoropropylcyclopentane sulfonate (PFPCPeS) were identified in environmental samples. The sum of PFECHS and PFPCPeS isomers displayed logarithmically decreasing spatial trends in water (1.04 - 324 ng/L) and sediment samples ( 0.194; p < 0.01). Similar to legacy PFASs, C8 Cl-PFESA levels in male serum samples (3.25 ng/g) were significantly higher than those in female serum samples (2.88 ng/g; p < 0.05). The lowest concentrations of C8 Cl-PFESA and legacy PFASs were both observed in the young female sub-population. Furthermore, based on the comparison of estimated daily intake by different exposure routes, it was concluded that diet is the primary source of Cl-PFESAs to general population in Shijiazhuang. Finally, we investigated the validity and applications of using hair, nail and urine samples for characterizing internal exposure to legacy and emerging PFASs. Biomonitoring samples from 8 highly exposed individuals showed that PFHxS, PFOS, C8 Cl-PFESA and PFUnDA were transferred from serum to nails in a dose dependent manner (ρ > 0.74; p < 0.05). Passive uptake experiments demonstrated that only lower than 6% of spiked PFASs were absorbed in hair and nail matrices from standard solutions (10, 100 and 1000 ng/g). Meanwhile, no uptake of PFASs in hair occurred over 56 days of contact with naturally contaminated indoor dust and air. Measurements of PFOS and C8 Cl-PFESA in hair and nail samples in a background exposed population displayed a plausible link to internal exposure by evaluation of statistical correlations with urine measurements and comparison with transfer ratios determined in highly exposed individuals.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/38711
Appears in Collections:环境化学与生态毒理学国家重点实验室_学位论文

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作者单位: 1.中国科学院生态环境研究中心
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