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题名: 毒杀芬分析方法及其环境污染特征研究
作者: 张兵
学位类别: 博士
答辩日期: 2012
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 郑明辉
关键词: 毒杀芬 ; Toxaphene ; 三重四级串联质谱仪 ; Triple quadrupole mass spectrometry ; 全二维气相色谱 ; Two-dimensional chromatography ; 同类物分布 ; Contamination distribution ; 单体特征 ; Congener profile
其他题名: Study on Analytical Method and Contamination Characteristics of Toxaphene in the Environment in China
中文摘要:     毒杀芬是一种组成复杂的有机氯农药,被列为《斯德哥尔摩公约》首批控制的持久性有机污染物。由于它的同类物数量众多,环境介质中毒杀芬的分析一直是环境科学学者面临的难点。本论文建立了针对不同介质的毒杀芬同类物的分析方法;并利用建立的方法首次对我国多种环境介质中毒杀芬的残留水平及污染特征进行了系统的研究。本文主要研究内容及结果如下: 1. 建立了同位素稀释-三重四级串联质谱多反应模式(MRM)测定大气、土壤、沉积物和生物样品中指示性毒杀芬(P26、P50和P62)的检测方法,该方法测定3种指示性毒杀芬,平均响应因子的相对标准偏差均小于< 15%,校正曲线在10~200 µg•L-1范围内显示良好的线性关系(r2>0.997)。方法检出限(S/N=3)为0.5~6 µg•L-1,满足痕量指示性毒杀芬的分析需求,为指示性毒杀芬的研究提供了定量和定性更准确的分析方法。 2. 鉴于毒杀芬同类物的复杂性,建立了全二维气相色谱电子捕获检测器分析毒杀芬同类物的检测方法,通过色谱条件的优化,对目前国际高度关注的23种毒杀芬同类物进行定性和定量分析。基质加标校正曲线在1~200 μg L-1浓度范围内,各毒杀芬同类物的线性相关系数(r2)均大于0.99。该方法检出限(S/N=3)为0.039~0.482 μg L-1,基质加标毒杀芬同类物的回收率为55~115%,相对标准偏差(RSD)均小于30%(n=5)。 3. 利用建立的方法首次系统地对我国环境背景中的毒杀芬残留水平进行了研究。首先,根据履约成效评估的需要,对我国8个大气背景点的大气样品进行了分析,分析结果表明,在背景大气中未检测到指示性毒杀芬的残留(检出限:P26<0.2, P50<0.5, P62<0.8 pg m-3,回收率:70~85%之间)。同时,在我国曾经使用毒杀芬的多个省份以网格布点的方式采集了769个土壤样品,还在我国的松辽流域、海河流域、黄河流域、长江流域和珠江流域采集了71个河流沉积物样品,并对所采集的样品进行了分析。分析结果表明,在被调查区域内,所有样品中均未检出毒杀芬的残留。由此可以推断我国毒杀芬的环境背景中残存水平很低。 4. 为了评估毒杀芬污染场地对周边环境产生的影响,对我国某原毒杀芬生产企业进行了多介质的样品采集与分析。从分析结果看,毒杀芬的总量在1.1~103 µg g-1之间,而土壤中的指示性毒杀芬的浓度与其他的同类物相比,处在较低水平,其中B8-1413(P26):0.54~11ng g-1、B9-1679(P50):3.0~44 ng g-1、B9-1025(P62):8.2~475 ng g-1,B9-2006的浓度最高,在33~2426 ng g-1之间,从植物样品的分析结果看,低氯代毒杀芬同类物所占比例较高。
英文摘要:    
    Toxaphene is a chlorinated insecticide that is a mixture of thousands of congeners. Because of its persistence, bioaccumulation, and inherent toxicity, toxaphene is now regarded as an organic chlorinated pollutant of concern worldwide, and is one of 12 persistent organic pollutants in the Stockholm Convention. The analysis of toxaphene is still a major challenge because of the numerous congeners it contains. In the present study, analytical methods for toxaphene congeners were developed in different media. The established methods were applied to determine the levels and distribution of toxaphene residues in the various environment compartments in China. The major results are summarized below. 1. Isotope dilution gas chromatography coupled to triple quadrupole mass spectrometry was developed to accurately identify and quantify indicator toxaphene congeners (P26, P50, P62) in environmental samples. The relative standard deviations (RSD) of the target compounds were all below 15 %. A good linear relationship (r2>0.997) was observed between 10–200 µg·L-1. The range for the limit of detection (S/N=3) was 0.5–6 µg·L-1. This analytical method meets the requirements for trace analysis of toxaphene congeners. 2. Because of the complexity of toxaphene congeners, comprehensive two-dimensional gas chromatography was coupled withmicro-electron capture detector for the simultaneous analysis of 23 toxaphene congeners. The major parameters for the gas chromatograph and modulator were optimized to improve the separation of target components. Sample matrix-matched calibration was used to determine the residue contents using external standard curves. The established method showed good linearity with correlation coefficients (r2) higher than 0.99 in the concentration range of 1–200 μg/L. The limit of detection (S/N=3) ranged from 0.039 to 0.482 μg/L for individual congeners, which indicates the method has high sensitivity. The relative standard deviations of all congeners in the matrix samples were below 30 % (n = 5), and the recoveries ranged from 55 to 115 %. 3. The toxaphene contamination status in different environmental compartments in China was systematically investigated with the developed method. Eight air background sites were selected to represent mainland China according to the Guidance on the Global Monitoring Plan (GMP). Toxaphene levels were below the LOD at the background sites (detection limits P26<0.2, P50<0.5, P62<0.8 pg m-3; recovery 70–85 %). Surface soil samples (n = 769) were collected with a grid collection method from Liaoning, Jiangsu and Zhejiang provinces (China) where toxapene had been used in the past. Sediment samples (n = 71) were collected from five river basins, including the Songliao, Hai, Yellow, Yangtze and Pearl River basins. The toxaphene levels in all samples were below the LOD. To evaluate the currant toxaphene contamination status, different types of samples were collected from a former toxaphene manufacturing plant in China. Ten samples were collected, including six soil samples and four plant samples. Toxaphene congeners were analyzed by comprehensive two-dimensional gas chromatography. The total toxaphene concentration ranged from 1.1 to 103 µg g-1. Among the 23 congeners, the nonachlorobornane B9-2006 congener was the most abundant in the soil samples with a concentration range of 33–2426 ng g-1. The indicator congener concentrations were low compared with the other congeners, as follows: B8-1413 (P26), 0.54–11 ng g-1; B9-1679 (P50), 3.0–44 ng g-1; and B9-1025 (P62), 8.2–475 ng g-1. The lower chlorinated homologs were predominant in the plant samples.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/35105
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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Recommended Citation:
张兵. 毒杀芬分析方法及其环境污染特征研究[D]. 北京. 中国科学院研究生院. 2012.
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