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题名: 短链和中链氯化石蜡的分析方法及人体暴露水平研究
作者: 夏丹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: 郑明辉 ; 高丽荣
关键词: 短链和中链氯化石蜡,全二维气相色谱,母乳,污染特征,暴露风险 ; Short-chain chlorinated paraffin, Medium-chain chlorinated paraffin, C9 chlorinated paraffin, Two-dimensional gas chromatography, Human breast milk, Infant health risk
其他题名: Analytical Method and Human Exposure of Short- and Medium-Chain Chlorinated Paraffins
学位专业: 环境科学
中文摘要: 氯化石蜡(CPs)是一类组成复杂的正构烷烃的氯代衍生物,其中短链氯化 石蜡(SCCPs)及中链氯化石蜡(MCCPs)均具有典型持久性有机污染物(POPs) 的特征,是近年来备受关注的一类新型的有机污染物。SCCPs已于 2017年 5月 被正式列入《关于持久性有机污染物的斯德哥尔摩公约》受控名单。CPs的组成 复杂,同类物和同分异构体总数愈万种,环境介质中 CPs的分离分析十分困难。 并且,由于 CPs的广泛生产和使用,CPs在多种环境和生物介质中广泛存在。然 而到目前为止,有关 CPs的人体暴露水平和健康风险的研究仍十分匮乏。本论文 针对 SCCPs和 MCCPs定量存在的问题,开展了 SCCPs和 MCCPs的全二维气相 色谱质谱定量分析方法研究,在此基础上研究了我国居民 SCCPs和 MCCPs的人 体内暴露水平、暴露途径以及健康风险。 1.通过优化色谱和质谱条件,建立了全二维气相色谱电子捕获检测器 (GC×GC-μECD)和全二维气相色谱-负化学电离源-高分辨飞行时间质谱 (GC×GC-ECNI-HRTOF-MS)定性定量分析 SCCPs和 MCCPs的方法,本方法 极大地改善了不同碳链长度、不同氯取代氯化石蜡同类物的色谱分离度,实现了 SCCPs和 MCCPs的色谱分离,去除了来自 CPs同类物之间的相互定量干扰。同 时有效去除了其他相似 POPs(如毒杀芬、多氯联苯和多溴二苯醚等)在 CPs定 量上存在的干扰,实现了 48种 SCCPs和 MCCPs同类物的定量分析。将方法应 用至沉积物和生物样品等多种环境介质中 SCCPs和 MCCPs的分析测定,方法回 收率和重现性良好,SCCPs和 MCCPs的方法检出限分别为 5.6 ng/g和 2.0 ng/g。 本方法为环境样品中 SCCPs和 MCCPs的定量分析提供了新的思路。 2.利用建立的定量分析方法,研究了我国城市和农村地区居民母乳中 SCCPs和 MCCPs的污染水平和分布特征。按照世界卫生组织和联合国环境规划 署全球母乳 POPs监测导则的指导,于 2007和 2011年在我国 16个省市城市和 农村地区采集居民母乳样品。样品分析结果表明,SCCPs和 MCCPs在母乳样品 中普遍检出,并且部分省市居民 SCCPs处于较高的污染水平,这可能与 CPs工 业的生产和使用有关。城市母乳中 CPs的污染水平高于农村母乳,并且 2007年 到 2011年期间,我国母乳中 SCCPs和 MCCPs的暴露水平呈明显增加趋势。目 前我国婴儿经母乳喂养摄入 CPs不足以构成明显的人体健康风险,但随着污染 水平的持续增加,我国 CPs带来的人群暴露健康风险应该引起持续关注。 3.利用 GC×GC-ECNI-HRTOF-MS分析技术,首次在实际土壤和鱼体环境介 质中鉴别出碳链长度更短的氯化石蜡(C9-CPs)。开展了 C9-CPs在我国 CPs工业 产品中的赋存状况以及不同环境介质中 C9-CPs浓度及同类物组成研究。结果显 示,C9-CPs在我国不同 CPs工业品中和大气、土壤等环境介质中广泛存在,并 易于在生物体富集。对南极地区多种介质样品的分析结果表明 C9-CPs具有长距 离迁移能力,是一类全球性的环境污染物。考虑到我国 CPs的巨大生产量,C9- CPs的环境行为有待进一步深入,以期为研究 C9-CPs在大规模尺度上的环境迁 移规律和潜在的生态风险积累数据。
英文摘要: Chlorinated paraffins (CPs) are complex technical mixtures containing thousands of isomers. Short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) have properties similar to persistent organic pollutants, such as toxicity, persistence, and the potential to undergo long-range transport and bioaccumulate. SCCPs have been listed as persistent organic pollutants under the Stockholm Convention since May 2017. However, methods for accurately analyzing CPs are not well developed because of difficulties with their separation and quantification. Comprehensive two-dimensional gas chromatography (GC×GC) can be used to separate CPs with a high degree of orthogonality. In this study, we developed a quantitative method for analysis of SCCPs and MCCPs using GC×GC, and then investigated the exposure levels, distributions, and sources of SCCPs and MCCPs in human breast milk in China. 1. New, sensitive, and effective methods for simultaneously profiling and quantifying SCCPs and MCCPs have been developed using GC×GC coupled to micro electron capture detection (GC×GC-μECD) and electron capture negative ionization high-resolution time-of-flight mass spectrometry (GC×GC-ECNI-HRTOF-MS). Using this method, 48 CPs formula groups were analyzed with high selectively in one injection using accurate mass measurements of [M−Cl]− ions in full scan mode. The correlation coefficients (R2) for the linear calibration curves for different chlorine contents were 0.98 for SCCPs and 0.94 for MCCPs. The method was successfully used to analyze CPs in sediment and fish samples. The good chromatographic separation and high mass resolution of this method minimized interferences between CPs congeners and other organohalogen compounds, such as PCBs, PBDEs and toxaphenes. This method is a powerful tool for the analysis of CPs in environmental samples. 2. The established method was applied to investigate the exposure levels, distributions, and sources of SCCPs and MCCPs in human breast milk. Samples of breast milk were collected from individuals in urban and rural areas in 12 Chinese provinces in 2007 and in 16 provinces in 2011. High CPs concentrations were found in the breast milk samples, with variations of more than two orders of magnitude in CPs exposure levels between different provinces. There are probably multiple CPs sources for the general population in China and numerous exposure pathways. The concentrations of the CPs increased from 2007 to 2011, which indicates that CPs production and use may be an important exposure source. The increasing concentrations of CPs in human breast milk indicate that continuous monitoring is required. 3. New CPs with the formulas C9H14Cl6 and C9H13Cl7 were identified and quantified in various environmental matrices for the first time. The possible sources, occurrences, and fates of these C9-CPs in environmental matrices were investigated. The octanol–air partition coefficients, octanol–water partition coefficients, bioaccumulation factors, and environmental fates of the C9-CPs were predicted using quantitative structure–property relationship models. The C9-CPs were also determined in various environmental matrices to obtain an understanding of their sources and occurrences. The detection of C9-CPs in sediment and indoor air samples suggests that C9-CPs are ubiquitous in various environmental matrices. The prevalence of C9-CPs in industrial products indicates that the production and use of these products has contributed to their presence in the environment. EPI Suite modeling results and the concentrations found in different environmental matrices indicate that C9-CPs have the potential to undergo long-range transport and bioaccumulate. Therefore, further assessments of the environmental fates and behaviors of C9-CPs in environmental matrices on a global scale are required.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/38712
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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