Quantitative Determination Of Perfluorooctane Sulfonyl Fluoride By LC/MS And The Application In Environment Analysis

Perfluorooctane sulfonyl fluoride (PFOSF), as a main precursor of perfluorooctane sulfonate(PFOS), is ubiquitous in the environment. PFOSF has been worldwide used in various fields such as industrial polymer, textile, dyeing, firefighting foams, leather, food packaging and so on, because of its unique and useful chemical properties including surface activity, thermal and acid resistance, as well as repellency of water and oil. PFOSF is endowed with the existence of the carbon-fluorine bond, one of the strongest bonds found in organic chemistry, with great chemical stability and resistant to degrade in typical environmental degradation processes, neither of chemical degradation or biodegradation. Furthermore, PFOSF has been confirmed with high bioaccumulation and biomagnification. So far, PFOSF has been volatile with an estimated global direct or indirect release of 45,250 tons to the soil, waters and atmosphere, which had a threat to the environment. Besides, PFOSF is of biotoxicity and the ability of long-range transport. Hence, PFOSF, PFOA and PFOS were added as POPs in Annex B of the Stockholm Convention in 2009. PFOSF cannot be directly analyzed by using liquid chromatography tandem mass spectrometry due to the lack of ionizable functional groups and chromophore in the molecule. The research about the content of PFOSF in different environmental samples was still the blank. This thesis mainly discussed that quantitative determination of PFOSF by LC/MS and the application in environment analysis.The thesis was mainly divided into the following three parts:1. The thesis gave an overview of the research process of perfluorinated compounds(PFCs), including the summarization of production, structure, types, properties, applications, toxicity, global transport theory, and human health risk assessment. We also summarized the research progress on PFCs sample pretreatments and instrumental, analysis, the content of PFCs in various environmental media, as well as the the research progress of PFOSF.2. A sensitive and accurate redox derivatization methodology for quantitative analysis detection of PFOSF was developed by LC-MS/MS. A series of organic reductants and catalysts were investigated, and finally, redox-dependent modification of PFOSF with p-toluenethiol and triethylamine led to the formation of perfluorooctane sulfinic acid. In addition, the dosages of p-toluenethiol and triethylamine, the derivatization time, as well as the detection condition of LC-MS/MS were investigated. PFOSF presented good linearity in the range from 0.5 to 200 ng/mL, with r2 of 0.9991, and the detection limit of PFOSF was 0.1 pg.3. The enrichment and detection procedures of PFOSF in environmental water were developed:liquid-liquid extraction method along with p-toluenethiol as derivatization reagent. In the meantime, the standard addition calibration method was utilized in the analysis of LC-MS water, tap water and Yunhe. As a result, the mean concentrations of PFOSF in tap water, which collected from different days, was from 1330 to 1700 ng/L, the mean concentrations of PFOSF in YunHe was 850 ng/L, and 500 ng/L for LC-MS water. It turned out that PFOSF was ubiquitous in environmental water, and its content was much higher than in LC-MS water. The derivatization procedure combined with LLE enabled the analysis of PFOSF in water, and the detection limit of the exctraction was 0.5 pg.