全氟辛基磺酰氟的液质联用检测方法研究及其在环境分析中的应用

发布时间：2018-03-19 09:37

本文选题：全氟辛基磺酰氟　切入点：衍生化反应　出处：《浙江大学》2017年硕士论文　论文类型：学位论文

【摘要】：全氟辛基磺酰氟(Perfluorooctane sulfonyl fluoride, PFOSF),是全氟辛基磺酸类化合物的主要前体。PFOSF因具有特殊的化学性质,表面活性、热稳定性、耐酸性以及疏水疏油性,而广泛应用于生产与生活中如纺织品涂层、染色剂、泡沫灭火器、皮革等行业。PFOSF具有键能最强的C-F键,其极大的稳定性导致该类化合物难以在环境介质中化学降解及生物降解；并且可在生物体内放大、富集。截至目前有高达45250吨的PFOSF直接或间接排放到土壤、水体、大气中,对环境造成较大威胁。此类化合物具有远距离迁移能力和一定的生物毒性,因此在2009年,全氟辛烷磺酰氟、全氟辛烷磺酸及其盐类、全氟辛酸及其盐类作为新型持久性有机污染物(POPs)被添加到《斯德哥尔摩公约》的附件B中。PFOSF由于其结构的特殊性,分子中缺乏可离子化基团及发色团,难以通过液相色谱质谱联用技术(LC/MS)对其进行分析检测。有关此类化合物在环境样品中的含量研究尚属空白。论文着重探讨PFOSF的LC/MS检测方法及其在环境样品分析中的应用。本论文主要分为以下三个部分：1.首先对全氟化合物进行综述,主要概述了全氟化合物的生产方式、结构、种类、性质、用途、毒性、人类健康风险评估、全球传输理论,并且对全氟化合物的样品前处理方法、仪器分析研究进展、不同环境介质中的分布情况进行了概述。同时,对PFOSF的生产、性质、用途,以及国内外研究进展进行概述。2.以PFOSF作为主要研究对象,建立其氧化还原衍生化方法,进而通过LC-MS/MS技术对此类化合物进行定量分析检测。实验对不同衍生化试剂以及催化剂进行比较,最终优选出对甲苯硫酚作为衍生化试剂、三乙胺作为催化剂。此外,本文考察了对甲苯硫酚、三乙胺的用量以及衍生化时间对产率的影响,并优化了LC-MS/MS方法的检测条件,进而实现该化合物的定量分析检测。考察了方法的适用性获得了较好的实验结果,PFOSF的线性检测范围为0.5-200 ng/mL,线性相关系数r2为0.9991,检出限为0.1 pg。3.环境水体中PFOSF的富集及检测：采用液-液萃取方式,对甲苯硫酚作为衍生化试剂,通过标准加入法对色谱质谱级纯水、自来水、运河水进行检测。结果显示不同时间所采集的自来水中PFOSF的平均含量为：1330-1700 ng/L;运河水中PFOSF的平均含量为850 ng/L;色谱质谱级纯水中平均含量为500 ng/L。结果表明环境水体中普遍含有PFOSF,且明显高于色谱质谱级纯水。同时对方法进行验证,检出限为0.5 Pg,在低、中、高三个不同浓度水平的重复性RSD分别为10.88%,10.45%,8.45%。
[Abstract]:Perfluorooctane sulfonyl fluorofluorooctane (PFOSF) is the main precursor of perfluorooctane sulfonic acid compounds. PFOSF has special chemical properties, surface activity, thermal stability, acid resistance and hydrophobicity. PFOSF is widely used in textile coating, dyeing agent, foam fire extinguisher, leather and other industries. PFOSF has the strongest bond energy C-F bond, and its great stability makes it difficult to degrade this kind of compounds in environmental media. Up to now, up to 45250 tons of PFOSF has been directly or indirectly discharged into soil, water and atmosphere, which pose a great threat to the environment. Thus, in 2009, perfluorooctanesulfonyl fluoride, perfluorooctane sulfonic acid and its salts, perfluorooctanoic acid and their salts as new persistent organic pollutants, were added to Annex B of the Stockholm Convention. PFOSF was added to Annex B of the Stockholm Convention because of its structural specificity, The lack of ionization groups and chromophore in the molecules, It is difficult to analyze and detect PFOSF by liquid chromatography-mass spectrometry (LC / MS). The study on the content of these compounds in environmental samples is still blank. This paper focuses on the LC/MS detection method of PFOSF and its application in the analysis of environmental samples. This paper is divided into the following three parts: 1.First, a review of perfluorocarbons, The methods of production, structure, species, properties, uses, toxicity, human health risk assessment, global transport theory, sample pretreatment methods and instrumental analysis of perfluorinated compounds are reviewed. At the same time, the production, properties, uses and research progress of PFOSF are summarized. 2. Taking PFOSF as the main research object, the method of redox derivation is established. Then the quantitative analysis of these compounds was carried out by LC-MS/MS. Finally, p-methylthiophenol and triethylamine were selected as derivatization reagent and triethylamine as catalyst by comparing different derivatization reagents and catalysts. In this paper, the effects of the dosage of p-methylthiophenol, triethylamine and derivatization time on the yield were investigated, and the detection conditions of LC-MS/MS method were optimized. The linear detection range of PFOSF is 0.5-200 ng / mL, the linear correlation coefficient R2 is 0.9991, the detection limit is 0.1pg.3. the enrichment of PFOSF in environmental water is obtained. And detection: liquid-liquid extraction, As a derivatization reagent, p-methylthiophenol was used for the determination of pure water and tap water in chromatography-mass spectrometry by standard addition method. The results show that the average content of PFOSF in tap water collected at different times is 1: 1330-1700 ng / L; the average content of PFOSF in canal water is 850 ng / L; the average content in pure water of chromatography-mass spectrometry is 500ng / L. the results show that the average content of PFOSF in environmental water is 500ng / L. It contains PFOSFs and is obviously higher than pure water in chromatography-mass spectrometry. The detection limit was 0. 5 PG, and the reproducibility RSD of three different concentrations in low, middle and high levels were 10. 88 and 10. 45 and 8. 45, respectively.
【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.63;X830

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