RCEES OpenIR  > 环境水质学国家重点实验室
水体中半挥发性有机污染物的非目标筛查方法及应用
Alternative TitleDevelopment and application of non-target screening method for the analysis of semi-volatile organic compounds in aqueous environment
徐雄
Subtype博士
Thesis Advisor王子健 ; 王东红
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半挥发性有机污染物,全二维气相色谱质谱,非目标分析,消毒副产物 Semi-volatile Organic Compounds, Comprehensive Two Dimensional Gas Chromatography-quadrupole Mass Spectrometry, Non-target Analysis, Disinfection By-products.
Abstract

      环境中的未知有机污染物分析一直以来是人们的研究重点。近年来新兴有机污染物(EOCs)不断地在各环境介质中被检出,种类和数量均不断增加。由于受到目标分析方法的限制,对未知有机污染物的甄别进展缓慢,使我们对环境污染的认识局限于预先选择的化合物。在此背景下,本论文首先针对水体中的半挥发性有机污染物,建立了基于全二维气相色谱质谱(GC×GC-qMS)仪器分析方法,在数据甄别流程中引入了保留指数作为定性判定工具,最终建立了适用于水体中半挥发性有机污染物的非目标分析方法。本论文将此方法应用到了地表水半挥发性有机污染物的非目标分析和饮用水中未知消毒副产物的鉴定中。

      首先,本论文分析方法应用于流域地表水中有机污染物的非目标分析中。在27个地表水样品中共定性检出239种高可信度化合物,按用途可分为化工原料、药物和个人护理品及农药等6大类,研究发现化工原料类化合物种类最多,并且239种定性检出化合物中有72%为首次在地表水中报道;对其中的149种进行了标准品对照,结果显示定性对照的准确性为100%。在定量分析的基础上,计算了107种具有潜在毒性的化合物的风险商,最终在流域尺度上得到了30种具有潜在风险的化合物,其生态风险值得进一步研究。

      更进一步运用该方法对研究了PAHs在加氯消毒过程中的转化规律及产物鉴定。在基于GC×GC-qMS的非目标分析方法基础上,对PAHs的加氯消毒产物进行了全分析。结果表明,在八种原水中常见的PAHs中,苊烯、苊、蒽和芘表现出了较强的反应活性,在水厂加氯消毒过程中更容易成为PAHs类消毒副产物的前驱体。苊烯和蒽的主产物为氧化PAHs,苊和芘的主产物为氯代PAHs,产物类型差异的原因是反应机理的不同;苊烯和蒽经历的是单电子转移机理,而苊和芘是亲电取代反应。结合Fukui函数值和GC×GC-qMS定性分析结果,成功推导了苊和芘的氯代反应路径,并使用合成的标准品进行了对照确认。针对以上四种PAHs,GC×GC-qMS非目标分析共找到了28种与之相关的消毒副产物,其中19种为首次报道。

      本研究建立了基于GC×GC-qMS的非目标分析方法,并成功应用到了地表水中半挥发性有机污染物和PAHs在加氯消毒过程中的产物鉴定中。此方法为环境中半挥发性有机污染物的非目标分析及消毒副产物的鉴定提供了新思路。

Other Abstract

      The analysis of unknown organic pollutants in the environment has always been the focus of environmental chemists. In recent years, emerging organic contaminants (EOCs) have been detected in various environmental media, with both increasing numbers and classes. Due to the limitation of target analysis method, our understanding of environmental pollution by organic comtaminants is always hysteretic with the actual situation. Therefore, this thesis firstly established the instrumental method based on comprehensive two-dimensional gas chromatography (GC×GC-qMS) with emphasis on the non-target screening of semi-volatile compounds in aqueous environment, and incorporated retention index as a qualitative analysis tool during the data analysis procedure. This method is applied to the non-target analysis of semi-volatile organic compounds in surface water and the identification of the unknown disinfection by-products in drinking water during chlorination.

       Firstly, this thesis applied the non target analysis method to the screening of unknown organic pollutants in surface water of major basins in China. A total of 239 organic compounds with high confidence were detected in 27 surface water samples, which could be categorized in six major group such as industrial materials, pharmaceutical and personal care products and pesticides according to their application. 149 of them were confirmed with standard products, and the results showed that the accuracy of qualitative analysis was 100%. We selected 107 potential toxic compounds were selected for quantitative analysis, and on the basis of risk quotient, the ecological risk of the quantified compounds were evaluated. The results showed that 30 compounds posed potential ecological risk, which deserved further attention.

      Furthermore, the transformation and product identification of PAHs during chlorination disinfection were studied by using this method. The results show that amongst eight ubiquitous PAHs in raw water, acenaphthene, acenaphthylene, anthracene and pyrene manifested strong reactivity, and are more likely to be precursor of disinfection by-products of PAHs during drinking water chlorination process. The main products of acenaphthylene and anthracene are oxygenated PAHs, the main product of acenaphthene and pyrene are chlorinated PAHs. The difference product types suggested different reaction mechanism: acenaphthylene and anthracene undergoes single electron transfer mechanism, and acenaphthene and pyrene undergoes electrophilic substitution reaction. Based on the qualitative results of GC×GC-qMS and Fukui function, we successfully elucidated the chlorination pathway of acenaphthene and pyrene, several products were confirmed by synthetic reference materials. A total of 28 transformation products were identified for acenaphthylene, acenaphthene, anthracene and pyrene, of which 19 were reported for the first time.

      This manuscript developed a non-target analysis method based on GC×GC-qMS, which was successfully applied to the non-target analysis of semi-volatile organic contaminates in surface water and the identification of the transformation byproducts of PAHs during aqueous chlorination. The methodology developed in this study provides a new solution for the non-target analysis of environmental contaminants and the identification of disinfection byproducts.

Pages135
Language中文
Document Type学位论文
Identifierhttp://ir.rcees.ac.cn/handle/311016/41595
Collection环境水质学国家重点实验室
Recommended Citation
GB/T 7714
徐雄. 水体中半挥发性有机污染物的非目标筛查方法及应用[D]. 北京. 中国科学院生态环境研究中心,2018.
Files in This Item:
File Name/Size DocType Version Access License
徐雄-水体中半挥发性有机污染物的非目标筛(6698KB)学位论文 开放获取CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[徐雄]'s Articles
Baidu academic
Similar articles in Baidu academic
[徐雄]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[徐雄]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.