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题名: 环境介质中新型芳香族有机污染物的发现及其行为研究
作者: 刘润增
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 ; 阮挺
关键词: 新型芳香族有机污染物、合成酚类抗氧剂、光引发剂、苯并三唑类紫外线吸收剂 ; emerging aromatic organic contaminants, synthetic phenolic antioxidants, photoinitiators, benzotriazole UV stabilizers
其他题名: Occurrence and Behaviors of Emerging Aromatic Organic Contaminants in the Environment
学位专业: 环境科学
中文摘要:       随着化学品的大量生产和应用,越来越多的有机污染物出现在环境介质中,对生态安全和人体健康造成了潜在危害,如何寻找环境介质中的新型有机污染物成为环境科学领域的一项重要工作。芳香族化合物在有机化合物的合成和使用中占有重要地位,并且由于苯环的存在使得许多芳香族合物的环境稳定性和生物毒性较强,因此我们重点关注环境中的新型芳香族污染物。本论文以芳香族的抗氧剂、光引发剂和紫外线吸收剂为研究对象,对这三类污染物的分析方法、区域污染现状、环境行为和人体暴露等进行了研究。
      合成酚类抗氧剂(synthetic phenolic antioxidants, SPAs)是目前应用最为广泛的人造抗氧剂。针对环境水体中的SPAs,我们开发了液液萃取和硅胶净化的前处理手段;而对于污泥中的SPAs,我们建立了加速溶剂萃取、硅胶净化、稀释进样的前处理方法。目标物的测定使用高效液相色谱-串联质谱,采用ESI负离子模式。污水处理厂能够收集较大区域内的工业和生活废水,因此污泥是考察大区域尺度有机污染物污染现状的理想介质。运用所建立的方法,我们对采自全国的56个污泥样品进行了测定,结果显示11种目标物质有检出,浓度最高可以达到30.3 μg/g。污泥样品中SPAs的总浓度范围是183 ng/g-41.0 μg/g,平均值为4.96 μg/g。污泥样品中SPAs的组成中2,6-di-tert-butyl-4-methylphenol (BHT)占主导,占SPAs总浓度的83.4%。这些SPAs单体的高比率和高浓度的检出说明它们在中国具有广泛的应用。此外,我们考察了污水处理厂二级活性污泥系统(厌氧-缺氧-好氧)对SPAs的去除效率,结果发现SPAs在该二级处理系统中的去除效率较高,为80.1-89.2%。但是,BHT去除的同时有三种转化产物大量生成。另外,我们还考察了室内灰尘中SPAs的污染现状。结果显示有7种SPAs单体在室内灰尘中有检出,浓度范围是       光引发剂(photoinitiators, PIs)是一类重要的人造化学品,其主要作用是在光照条件下产生活性物质,例如自由基,从而引发聚合反应。根据光引发剂分子结构的不同,最常使用的光引发剂可以被分为苯酮类(benzophenones,BZPs)、硫杂蒽酮类(thioxanthones,TXs)和胺类共引发剂(amine co-initiators,ACIs)。我们的实验表明PIs广泛存在于我们所采集的商品样品中,在食品包装材料和光敏树脂3D打印产品中,ΣPIs的浓度范围分别为69.5-6.93e3 ng/g (GM: 319 ng/g)和655-2.51e4 ng/g (GM: 3.84e3 ng/g)。这些含有PIs的商品在室内环境中被广泛使用,导致室内灰尘中ΣPIs的几何平均浓度高达610 ng/g。此外,21种PIs的单体在污泥样品中均有检出,其中19种单体是首次被发现。60个污泥样品中ΣPIs的浓度范围是67.6-2.03e3 ng/g,几何平均值为301 ng/g。BZPs是最主要的污染物质,在60个污泥样品中,其浓度占PIs总浓度的9.01-97.0%,平均占比为77.0%。ACIs和TXs的浓度相对较低,占PIs总浓度的平均值分别为13.1%和10.0%。层序聚类分析的结果显示不同地域之间PIs的污染不存在明显的差别,这说明PIs在我国环境中存在着普遍的污染。我们使用Toxtree软件对PIs的毒性进行了初步的预测,结果显示多数PIs单体属于毒性级别最高的III类,并且有些单体还可能具有基因毒性。这是首次报道环境介质中PIs的污染。
      针对水体中的苯并三唑类紫外线吸收剂(benzotriazole UV stabilizers,BZTs),我们开发了在线固相萃取-高效液相色谱-串联质谱的测定方法。对测定过程中影响目标物回收率的影响因素如固相萃取柱的种类、上样速度、水样的酸碱度、水样中甲醇的含量等进行了考察。我们所建立的方法的检测限为0.21-2.17 ng/L,目标物的加标回收率为76.1-114%。该方法具有简单、灵敏、高效的优点,适合于检测水体中的BZTs类污染物。运用所建立的方法,我们对所采集的河水和污水处理厂的污水样品进行了测定,结果在样品中检测出了5种BZTs的单体,浓度最高可以达到37.1 ng/L。
英文摘要:       Due to the large production and usage of organic chemicals, more and more contaminants of emerging concern were found in the environment, which bring potential harm on ecological safety and human health. Thus, identification of novel organic pollutants in the environment becomes an important work in the field of environmental science. Since aromatic chemicals play important roles in the chemical production and usage, and many aromatic substances are persistent and toxic, attention was paid on the occurrence of novel aromatic organic pollutants in the environmental matrix. In the present study, three kinds of aromatic chemicals including antioxidants, photo-initiators and UV stabilizers were investigated for their analytical methods, environmental pollution, behaviors in the environment and human exposure.
      Synthetic phenolic antioxidants (SPAs) are the most widely used manmade antioxidants. For the water sample analysis, liquid-liquid extraction combined with silica gel cleanup was developed. For the sludge sample analysis, accelerated solvent extraction, silica cleanup and dilution injection method was built. The targets were determined by optimized high performance liquid chromatography-tandem mass spectrometry method in negative electrospray ionization mode. Since wastewater treatment plant receives sewage input from vast domestic and/or industrial area, sewage sludge can be an excellent medium to track the occurrence of emerging organic pollutants at a large geographical scale. Using the developed analytical methods, 56 sludge samples were analyzed. Results showed that 11 targets could be positively identified, with concentrations up to 30.3 μg/g. Total concentrations of SPAs (ΣSPAs) in sludge samples ranged from 183 ng/g to 41.0 μg/g, with an average value of 4.96 μg/g. 2,6-Di-tert-butyl-4-methylphenol (BHT) was the most dominant SPA analogue, which constituted 83.4% of ΣSPAs. The high detection frequencies and concentrations of these SPAs demonstrated their wide usage in China. The activated sludge system (anaerobic, anoxic, and oxic tanks) of a wastewater treatment plant was further investigated for the removal efficiencies of the SPAs. High removal efficiencies (80.1-89.2%) were found for the six detected SPAs in the aqueous phase, while generation of large proportions of the three BHT metabolites was also observed. Besides, the occurrence of SPAs in indoor dust was also investigated. Results showed that 7 SPA analogues were found in the dust samples, with concentrations in the rang of       Photoinitiators (PIs) are anthropogenic chemicals, which are widely used to generate active substances such as free radicals, and to initiate polymerization during optical absorption process. With regard to molecular structures, the most frequently used PIs can be categorized as benzophenones (BZPs), thioxanthones (TXs), and amine co-initiators (ACIs). The present study demonstrated the existence of some PI analogues in commercial products including food contact materials and UV curable resin 3D printing products, with the concentrations of ΣPIs (sum of the detected PIs) in the range of 69.5-6.93e3 ng/g (GM: 319 ng/g) and 655-2.51e4 ng/g (GM: 3.84e3 ng/g), respectively. Due to the occurrence of PIs in commercial products and the prevalent usage of these products in households, high concentrations of ΣPIs (GM: 610 ng/g) were also found in indoor dust samples. Besides, all the 21 PIs analogues could be positively identified in the sludge samples, among which the occurrence and contamination levels of 19 chemicals were reported for the first time. BZPs were found as the dominant analogues, accounting for 9.01-97.0% (averaged proportion: 77.0%) of ΣPIs concentrations, whereas ACIs (13.1%) and TXs (10.0%) had comparable averaged proportions. Hierarchical cluster analysis (HCA) did not found obviously different target concentration groups among the sampling locations, which might indicate universality of PI usages and contamination in China. Most of the target PIs were further identified as class III chemicals by toxic hazard estimation algorithm (Toxtree). This is the first time to report the occurrence of PIs in the environment.
      A method using automated on-line solid phase extraction coupled with a high-performance liquid chromatography-tandem mass spectrometry system was developed for the determination of emerging benzotriazole UV stabilizers (BZTs) in different environmental water matrices. Experimental parameters such as sample loading flow rate, SPE cartridge, pH value and methanol ratio in the sample were optimized in detail. The method detection limits ranged from 0.21 to 2.17 ng/L. Recoveries of the target BZTs at 50 ng/L spiking level ranged from 76.1% to 114%. The proposed method is simple, sensitive and suitable for simultaneous analysis and monitoring of BZTs in water samples.The optimized method was successfully applied to analyze twelve water samples collected from different wastewater treatment plants and rivers, and five BZTs were detected with concentrations up to 37.1 ng/L.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/36897
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:
刘润增. 环境介质中新型芳香族有机污染物的发现及其行为研究[D]. 北京. 中国科学院研究生院. 2016.
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