JP-7855802-B2 - Method for measuring the concentrations of perfluoroalkyl and polyfluoroalkyl compounds, and liquid chromatography/tandem mass spectrometry system.

Inventors

• 王 亜 ▲ウェイ▼
• 何 安 恩
• 黎 娟
• 李 暁 東
• 郭 彦 麗
• 楊 暁 春
• 島 圭介
• 曹 磊

Assignees

• 中国科学院生▲態▼▲環▼境研究中心
• シマヅ （チャイナ） シーオー エルティーディー

Dates

Publication Date

20260508

Application Date

20230824

Priority Date

20220824

Claims (10)

1. A method for measuring the concentrations of perfluoroalkyl compounds and polyfluoroalkyl compounds, characterized in that the concentrations of perfluoroalkyl compounds and polyfluoroalkyl compounds, which include at least one perfluoroalkylphosphonic acid/phosphinic acid compound or polyfluoroalkyl phosphate ester compound, are measured in a single measurement by liquid chromatography/ tandem mass spectrometry, wherein a phenylhexyl column is used as the analytical column .
2. The method for measuring perfluoroalkyl compounds and polyfluoroalkyl compounds according to claim 1, characterized in that the alkaline mobile phase has a pH of 8 to 10.
3. The method for measuring the concentrations of perfluoroalkyl compounds and polyfluoroalkyl compounds according to claim 2, characterized in that the alkaline mobile phase has a pH of approximately 9.
4. The method for measuring perfluoroalkyl compounds and polyfluoroalkyl compounds according to claim 1, characterized in that the perfluoroalkyl compound and polyfluoroalkyl compound are a combination of multiple types selected from perfluoroalkyl carboxylic acid, perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonamide, perfluoroalkyl ether sulfonate , perfluoroalkyl ether carboxylic acid, perfluoroalkyl sulfonamide acetate, perfluoroalkylphosphonic acid, perfluoroalkylphosphinic acid , polyfluoroalkyl phosphate, fluorotelomer sulfonic acid, fluorotelomer carboxylic acid, and fluorotelomer betaine.
5. The method for measuring perfluoroalkyl compounds and polyfluoroalkyl compounds according to claim 1, characterized in that, in a single measurement, tandem mass spectrometry is used to switch between a positive ion scanning mode and a negative ion scanning mode depending on the type of perfluoroalkyl compound and polyfluoroalkyl compound being measured.
6. A liquid chromatograph/tandem mass spectrometry system, wherein the liquid chromatograph/tandem mass spectrometry system has a mode for measuring the concentrations of perfluoroalkyl compounds and polyfluoroalkyl compounds, and when the liquid chromatograph/tandem mass spectrometry system is operated in the mode for measuring the concentrations of perfluoroalkyl compounds and polyfluoroalkyl compounds, the system is configured to measure the concentrations of multiple types of perfluoroalkyl compounds and polyfluoroalkyl compounds in the sample, including at least one type of perfluoroalkylphosphonic acid/phosphinic acid compound or polyfluoroalkyl phosphate ester compound, in a single measurement in which the sample is eluted with an alkaline mobile phase, and the liquid chromatograph/tandem mass spectrometry system includes an analytical column, the analytical column being a phenylhexyl column .
7. The liquid chromatograph/tandem mass spectrometry system according to claim 6, characterized in that it has perfluoroalkyl compound and polyfluoroalkyl compound concentration measuring conduits, and the tubing material used for the perfluoroalkyl compound and polyfluoroalkyl compound measurement conduits is fluorine-free.
8. The liquid chromatograph/tandem mass spectrometry system according to claim 6, characterized in that it has a delay column installed between the liquid pump and the analysis column.
9. The liquid chromatograph/tandem mass spectrometry system according to claim 8, characterized in that the delay column is a C18 reversed-phase column.
10. The liquid chromatograph/tandem mass spectrometry system according to claim 6 is characterized in that it uses an electrospray ion source as the ion source for tandem mass spectrometry, the desolvation tube temperature of the electrospray ion source is 100 to 150°C, the heating module temperature is 200 to 250°C, and the interface temperature is 300 to 350°C.

Description

This invention relates to the field of analytical chemistry, and more specifically, to a method for measuring the concentrations of perfluoro and polyfluoroalkyl compounds, as well as a liquid chromatography/tandem mass spectrometry system. Perfluoroalkyl compounds and polyfluoroalkyl compounds (PFASs) are widely used in industry and manufacturing due to their high surface activity, thermal stability, hydrophobicity, and oleophobicity. PFASs, particularly perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), have attracted considerable attention due to their persistence, long-range transport, bioaccumulation, and potential toxicity. PFOS and PFOA are classified as persistent organic pollutants under the Swiss franc Convention, and their production and use are restricted. Furthermore, a wider variety of PFASs are being developed and produced as substitutes for PFOS and PFOA. Methods for detecting these potential risks in novel alternatives across different matrices have been reported in numerous research papers. Currently, many publications, standards, and regulations describe detection methods for perfluoroalkyl carboxylic acid compounds (PFCAs), perfluoroalkyl sulfonic acid compounds (PFSAs), perfluoroalkyl sulfonamide compounds (FASAs), etc. However, there are few relevant literature reports and limited detection methods for perfluoroalkylphosphonic acid (PFPAs) compounds, perfluoroalkylphosphinic acid (PFPis) compounds, and polyfluoroalkyl phosphate ester (PAPs) compounds. In their paper, "Measurement of Perfluoro and Polyfluorinated Compounds in Surface Water by Ultra-High Performance Liquid Chromatography Mass Spectrometry," published in the Chinese serial journal "Research Reports on Analytical Chemistry," 2018, vol. 9, p. 1400, Liu Xiaolei et al. disclosed an analytical method for measuring 23 types of PFASs, including perfluoroalkyl carboxylic acid compounds, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl phosphonic acid compounds, perfluoroalkyl phosphinic acid compounds, and polyfluoroalkyl phosphate diesters, in water using solid-phase extraction ultra-high performance liquid chromatography mass spectrometry. This analytical method involves using multiple parts of different mobile phases to elute the sample multiple times. In short, prior art lacks a method for simultaneously and rapidly measuring the concentrations of a wider variety of perfluoroalkyl and polyfluoroalkyl compounds, particularly a rapid method for measuring samples containing perfluoroalkylphosphonic acids, perfluoroalkylphosphinic acid compounds, or polyfluoroalkyl phosphate esters. This is a schematic diagram of the structure of an LC-MS/MS system according to an embodiment of the present invention.This is a chromatogram obtained by analyzing 93 types of PFASs in a single injection using the LC-MS/MS system of the embodiment of the present invention.This calibration curve was prepared using standard solutions with PFOA, PFOS, ADONA, and PFODA as the target substances, using the LC-MS/MS system of the embodiment of the present invention.This calibration curve was prepared using standard solutions with PFOA, PFOS, ADONA, and PFODA as the target substances, using the LC-MS/MS system of the embodiment of the present invention.This calibration curve was prepared using standard solutions with PFOA, PFOS, ADONA, and PFODA as the target substances, using the LC-MS/MS system of the embodiment of the present invention.This calibration curve was prepared using standard solutions with PFOA, PFOS, ADONA, and PFODA as the target substances, using the LC-MS/MS system of the embodiment of the present invention.This is a chromatogram obtained by analyzing 10 types of fluoritelomeric alcohol-based PFASs in a single injection using the GC-MS/MS system of the embodiment of the present invention. The technical proposal in this embodiment will be described clearly and completely below, in accordance with the drawings of this embodiment. However, it is clear that the embodiments described are only a part of the embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, those skilled in the art will know that all other embodiments, which can be obtained without creative work, also fall within the scope of protection of the present invention. 1. <Terms and their definitions> Perfluoroalkyl compounds and polyfluoroalkyl compounds are alkyl compounds in which all or more hydrogen atoms are replaced by fluorine atoms, and include several types of compounds such as perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acids, perfluoroalkyl sulfonamides, perfluoroalkyl ether sulfonates, perfluoroalkyl ether carboxylic acids, perfluoroalkyl sulfonamide vinegars, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, polyfluoroalkyl phosphates, and fluorotelomers (e.g., fluorotelomer alcohols, fluorotelomer sulfonic acids, fluorotelomer carboxylic acids, fluorotelome