Preparation And Application Of Perfluorinated Paper In Separation And Analysis Of Perfluorinated Compounds In Water Samples

Perfluorinated compounds(PFCs),as synthetic compounds,are widely used in textile,leather,coatings,pesticides and other daily necessities,they have toxic effect on ecosystem and human beings for their slowly biodegradable speed after heavy usage.At present,many pretreament methods have been reported in the literatures,including solid-phase extraction,liquid-liquid(micro)extraction,liquid-solid extraction,accelerated solvent extraction and other extraction methods.Excellent results have been obtained after those methods combined with detective instruments such as high performance liquid chromatography(HPLC),liquid chromatography-tandem mass spectrometry(HPLC-MS/MS),gas chromatography-tandem mass spectrometry(GC-MS/MS),gas chromatography-mass spectrometry(GC-MS)and ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS),which can be used to detect trace perfluorinated compounds existing in the environmental water samples and industial wastewater.However,typical limitations such as low detection limit?selectivity and complex derivatization operations are obvious,therefore,it is of great significance to develop a simple and economical and highly selectivity pretreatment method to combine with quick or highly sensitivity instruments for PFCs application in environmental water samples.In this paper,a rapid pretreatment for preparing fluorine-based paper as enrichment material has been developed.Due to the fluorine affinity,fluorine-based paper can be applied to the determination of four PFCs(including PFBA,PFOA,PFDA and PFOS)in environmental water samples and industrial wastewater by high performance liquid chromatography-mass spectrometry and ambient mass spectrometry,respectively.The main content of this paper is as follows:1.Preparation of fluorine-based paper by silylation.Trichloro(1H,1H,2H,2H-perfluorooctyl)silane(PFOTS)was the reagent that used to prepared fluorine-based paper.Concentration and reaction time of silylation reagent were investigated and the prepared modified paper was characterized with Fourier transform infrared spectra(FT-IR),water contact angle measurement(CA),scanning electron microscopy(SEM)and energy-dispersive X-ray spectroscopy(EDS),respectively.The results shows that fluorine-based paper can be successfully prepared in 0.1% PFOTS of N-hexane reagent within 4 minutes.The contact angle of the hydrophobic paper under the optimal conditions can reach 139°.The hydrophobicity of the modified paper could hardly change even if it was kept at room temperature for as long as three months.There are many advantages of the fluorine-based paper prepared by this method,such as simplicity,environmentally friendly,economical,strong hydrophobicity and stability.2.Fluorine-based paper was used as a solid phase extraction material to detect PFCs in environmental water samples by high performance liquid chromatography-mass spectrometry.Fluorine-based paper was used to separate and analyze the four perfluorinated compounds in Xiangjiang River water samples and tap water samples.The effects of quantity of fluorine-based paper,extraction time,pH value of water samples,desorption reagents and desorption time on extraction efficiency were investigated.The data showed that under the optimum experimental conditions,the target compounds and impurities can be completely separated within 12 minutes.The four PFCs were linearly related in the range of 0.2~5.0 ng/L,LOD were 0.04~0.05 ng/L and the recovery rate was 92.1%~101.5%,which verified that the feasibility of this method.Thus the fluorine-based paper can effectively separate and enrich trace PFCs in environmental water samples as an adsorbent.3.Fluorine based paper was used as a solid phase extraction material to detect four PFCs in industrial wastewater by ambient mass spectrometry.The fluorine-based paper was used to separate and analyze the target compounds in industrial wastewater.The effects of extraction time,pH value of water samples,ambient mass spectrometry spray voltage and cone voltage and matrix interference on the separation and analysis were investigated.The data showed that under the optimum experimental conditions,the four PFCs were linearly related in the range of 0.01~1 ?g/mL,LOD was 0.006 ?g/mL~0.027 ?g/mL,and the recovery rate was 75.3~93.5%.These results indicates that as an extraction material,fluorine-based paper combined with ambient mass spectrometry could be used as a preliminary technique to investigate PFCs content in industrial wastewater with complex substrates.