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Determination of eight per- and polyfluoroalkyl substances in seawater using dispersive membrane extraction-ultra-high performance liquid chromatography-tandem mass spectrometry
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Zhen REN1, Jiping MA1, *, Yajing LIU2, Lan ZHANG3, Gege WU1, Shuang LI1
Chinese Journal of Chromatography | 2025, 43(11) : 1235 - 1243
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Chinese Journal of Chromatography | 2025, 43(11): 1235-1243
• Articles •
Determination of eight per- and polyfluoroalkyl substances in seawater using dispersive membrane extraction-ultra-high performance liquid chromatography-tandem mass spectrometry
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Zhen REN1, Jiping MA1, *, Yajing LIU2, Lan ZHANG3, Gege WU1, Shuang LI1
Affiliations
  • 1. School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266520,China
  • 2. Qingdao Ecological Environment Monitoring Center of Shandong Province,Qingdao 266003,China
  • 3. Rizhao Quality Inspection and Testing Research Institute,Rizhao 276800,China
Published: 2025-11-08 doi: 10.3724/SP.J.1123.2025.04009
Outline
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Per- and polyfluoroalkyl substances (PFASs) are widely utilized in various industrial applications. Their persistence in ecosystems raises significant global environmental health concerns. Numerous studies have confirmed the toxicity of PFASs to human endocrine and immune systems. The carcinogenic risks associated with PFASs exposure increasingly alarm public health authorities worldwide. As a result, regulatory policies have been implemented to restrict both the production and environmental release of PFASs. In China, the GB 5749-2022 standard establishes stringent limits for PFASs concentrations in drinking water, capping levels of perfluorooctane sulfonic acid (PFOS) at 40 ng/L and perfluorooctanoic acid (PFOA) at 80 ng/L. Effective monitoring of PFASs requires advanced analytical techniques that exhibit exceptional sensitivity. Ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) has emerged as the preferred technique for detecting these substances due to its superior selectivity and low detection limits. However, complex environmental matrices necessitate optimized sample pretreatment strategies to enhance analysis accuracy. Efficient extraction methods must effectively address matrix interference while ensuring analyte enrichment. Dispersive membrane extraction (DME) presents distinct advantages for the pretreatment of PFASs; its operational simplicity is complemented by high enrichment capabilities and efficient mass transfer. The selection of extraction materials critically influences DME performance parameters. Metal-organic frameworks (MOFs) are porous materials composed of organic ligands and metal clusters, featuring tunable pores, high surface areas, and rapid mass transfer. These unique properties enable their current use in sample pretreatment for environmental analysis. This study integrates DME with UHPLC-MS/MS utilizing cationic MOF membranes, enabling simultaneous detection of eight different PFASs within seawater matrices. Optimized parameters ensure reliable quantification of trace-level contaminants throughout this process. The experimental design assessed various parameters, including types of organic solvents (methanol and acetonitrile), ammonium acetate concentrations in the aqueous phase (0.1, 0.5, 1.0, 2.0, and 5.0 mmol/L), as well as ion source voltages (-2 500, -3 500, and -4 500 V), all of which influenced detection efficacy. Chromatographic separation was performed using an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm). Gradient elution combined 1 mmol/L ammonium acetate with acetonitrile for optimal results. Detection was conducted utilizing electrospray ionization (ESI) in negative ion scanning mode coupled with multiple reaction monitoring (MRM). The results indicated that all eight PFASs could be effectively separated within a timeframe of 12 min, exhibiting favorable peak shapes and high response values. Under optimal conditions, the eight PFASs demonstrated strong linearity across their respective concentration ranges; the correlation coefficients (r²) were all not less than 0.990 7. Recoveries of PFASs at spiking levels of 10, 50, and 100 ng/L ranged from 50.4% to 116.4%, while intra-day and inter-day relative standard deviations (RSDs) varied from 1.0% to 19.2% and from 2.2% to 19.5%, respectively. The method’s limits of detection (LODs) ranged from approximately 0.07 ng/L to 0.49 ng/L, whereas the limits of quantification (LOQs) varied from around 0.22 ng/L to 1.63 ng/L. Jiaozhou Bay serves as a typical semi-enclosed bay along the Pacific coast where terrestrial runoff converges nutrients alongside diverse organic/inorganic pollutants that pose potential health risks for aquatic organisms inhabiting these waters. This method was utilized for the detection of the eight PFASs in the surface seawater of Jiaozhou Bay, and seven types were successfully identified. Among these, potassium 11-chloroeicosafluoro-3-oxaundecane-1-sulfonate (Minor F-53B) exhibited the highest detection concentration, with an average mass concentration of 17.11 ng/L. When compared to the 2018 detection results of PFASs in the surface seawater of Jiaozhou Bay, the average mass concentration of perfluorooctanoic acid (PFOA) has significantly decreased. Additionally, potassium 9-chlorohexadecafluoro-3-oxanonane-1-sulfonate (F-53B), one of the newly emerging PFASs, was detected in the surface seawater of Jiaozhou Bay, which may be attributed to the recent shift in PFASs production. The widespread use of these new PFASs may introduce environmental risks. These risks resemble those of traditional PFASs and require urgent attention. In summary, this method is operationally straightforward, rapid, and highly sensitive; it is suitable for analyzing the eight PFASs in seawater. This approach can provide a valuable data foundation and scientific basis for research and analysis concerning PFASs in environmental water bodies.

per- and polyfluoroalkyl substances (PFASs)  /  dispersive membrane extraction (DME)  /  cationic metal-organic framework  /  ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS)
任真, 马继平, 刘雅静, 张澜, 吴阁格, 李爽. 分散膜萃取-超高效液相色谱-串联质谱法测定海水中8种全氟及多氟烷基化合物. 色谱, 2025 , 43 (11) : 1235 -1243 . DOI: 10.3724/SP.J.1123.2025.04009
Zhen REN, Jiping MA, Yajing LIU, Lan ZHANG, Gege WU, Shuang LI. Determination of eight per- and polyfluoroalkyl substances in seawater using dispersive membrane extraction-ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2025 , 43 (11) : 1235 -1243 . DOI: 10.3724/SP.J.1123.2025.04009
  • National Natural Science Foundation of China(21976099)
  • Natural Science Foundation of Shandong Province of China(ZR2019MB046)
Year 2025 volume 43 Issue 11
36
18
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Article Info
doi: 10.3724/SP.J.1123.2025.04009
  • Receive Date:2025-04-07
  • Online Date:2026-10-30
  • Published:2025-11-08
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  • Received:2025-04-07
Funding
National Natural Science Foundation of China(21976099)
Natural Science Foundation of Shandong Province of China(ZR2019MB046)
Affiliations
    1. School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266520,China
    2. Qingdao Ecological Environment Monitoring Center of Shandong Province,Qingdao 266003,China
    3. Rizhao Quality Inspection and Testing Research Institute,Rizhao 276800,China
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表12种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
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Percentage of
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属
Genus
种数
Number of
species
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Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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