色谱

色谱 ›› 2025, Vol. 43 ›› Issue (6): 650-658.DOI: 10.3724/SP.J.1123.2024.08015

• 研究论文 • 上一篇    下一篇

磁固相萃取-液相色谱-质谱测定环境水样中全氟化合物及风险评估

谷晨舒1,2, 刘真真2, 金慧玲1,2, 刘小琦1,2, 王美玉1,2, 孙伟杰3,*(), 孙杨赢1,*(), 齐沛沛1,2,*()   

  1. 1.宁波大学食品科学与工程学院，省部共建农产品质量安全危害因子与风险防控国家重点实验室，浙江 宁波 315211
    2.浙江省农业科学院农产品质量安全与营养研究所，省部共建农产品质量安全危害因子与风险防控国家重点实验室，浙江 杭州 310021
    3.嘉兴市农业科学研究院桐乡农业科学研究所，浙江 嘉兴 314500
  • 收稿日期:2024-08-27 出版日期:2025-06-08 发布日期:2025-05-21
  • 通讯作者: * Tel：（0574）87609573，E-mail：sunyangying@nbu.edu.cn（孙杨赢）； Tel：（0571）86419051，E-mail：qipeipei@zaas.ac.cn（齐沛沛）； E-mail：11661075@qq.com（孙伟杰）.
  • 基金资助:
    浙江省重点研发项目(2023C02038)

Determination of perfluorinated compounds in environmental water samples by magnetic solid-phase extraction-liquid chromatography-mass spectrometry and associated risk assessment

GU Chenshu1,2, LIU Zhenzhen2, JIN Huiling1,2, LIU Xiaoqi1,2, WANG Meiyu1,2, SUN Weijie3,*(), SUN Yangying1,*(), QI Peipei1,2,*()   

  1. 1. State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products，School of Food Science and Engineering，Ningbo University，Ningbo 315211 China
    2. State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products，Institute of Agro-product Safety and Nutrition，Zhejiang Academy of Agricultural Sciences，Hangzhou 310021，China
    3. Tongxiang Institute of Agriculture Science，Jiaxing Academy of Agriculture Science，Tongxiang 314500，China
  • Received:2024-08-27 Online:2025-06-08 Published:2025-05-21
  • Supported by:
    Key Research and Development Program of Zhejiang Province(2023C02038)

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摘要：

全氟及多氟烷基化合物（PFCs）在全球环境水体中广泛存在。据报道，饮用水的摄入可能是人类接触PFCs的重要来源，因此亟需针对饮用水中PFCs的赋存特征、来源分析和风险评估进行深入的探究。本文以磁性聚苯乙烯-吡咯烷酮（Fe3O4-PLS）为磁性吸附剂，建立了水中11种PFCs富集的磁固相萃取方法，结合液相色谱-串联质谱（LC-MS/MS）分析，实现了水中PFCs的准确、灵敏测定。Fe3O4-PLS经甲醇活化后置于水溶液中，超声辅助萃取15 min，经磁分离后，采用乙腈（含0.1%甲酸）将目标物洗脱，洗脱液经氮吹复溶后进样分析。方法验证结果表明，11种PFCs在1～100 μg/L范围内线性关系良好，相关系数（R2）为0.997 6~0.999 9；检出限为0.001～0.620 ng/L，定量限为0.002～2.065 ng/L，方法灵敏度高。11种PFCs在不同添加水平（0.05、1、10、50 μg/L）下，回收率为60.8%～120.0%，相对标准偏差（RSD）为1.0%～20.0%，可满足水中PFCs的分析需求。采用该方法分析了杭州东苕溪15个点位（临近工厂、水库、居民区）样品中11种PFCs的残留浓度，共检测到6种PFCs，分别是全氟辛酸（PFOA）、全氟壬酸（PFNA）、全氟辛基磺酸（PFOS）、全氟庚基磺酸（PFHpS）、全氟丁基磺酸（PFBS）和全氟癸酸（PFDA），检出质量浓度为11.4~30.7 ng/L，其中全氟辛酸的质量浓度最高达到25.5 ng/L。东苕溪中PFCs主要来源于前体降解和工业废水排放，流域地表水中PFCs远低于官方给出的健康参考值，尚未达到对生态和人体产生风险的水平。

关键词: 磁固相萃取, 超高效液相色谱-串联质谱, 全氟化合物, 水

Abstract:

Perfluorinated compounds （PFCs） are widely used， persistent， and their presence in water is of significant concern. PFCs， particularly short-chain variants， are highly soluble and mobile in water， which enables their transport over long distances via river systems， potentially leading to extensive contamination. These compounds are resistant to degradation， which is challenging for conventional water-treatment methods that often remove PFCs ineffectively， leading to their prolonged presence in water bodies. This paper establishes a magnetic solid-phase extraction method for 11 PFCs in enriched water using magnetic polystyrene pyrrolidone （Fe3O4-PLS） as a magnetic adsorbent. Purified lipophilic PLS magnetic beads were used as the solid-phase extractant， and their surfaces were modified using phenyl and pyrrolidone groups to facilitate the adsorption of PFCs that contain hydrophilic functional groups and hydrophobic alkyl side chains. PFCs in water were determined accurately and sensitively by liquid chromatography-tandem mass spectrometry （LC-MS/MS）. The method involved accurately weighing 50 mg （±0.05 mg） of the Fe3O4-PLS into a 500-mL beaker， adding 2 mL of methanol （for activation）， placing the beaker on a magnet for 30 s， and discarding the methanol once the methanol and Fe3O4-PLS had been completely separated. A 200-mL aliquot of an aqueous mixed PFC solution was added to the beaker， sonicated for 15 min， and then placed on a strong magnet until the Fe3O4-PLS had completely separated at the bottom of the beaker. The upper liquid was discarded. A 4-mL acetonitrile containing 0.1% formic acid was added as the Fe3O4-PLS eluent， ultrasonicated for 30 s， after which the beaker was placed on the magnet and the eluate collected. The sample was taken to dryness under a stream of nitrogen， the residue was redissolved in 0.5 mL of acetonitrile， ultrasonicated for 10 s， and then membrane-filtered prior to analysis by LC-MS/MS. The 11 PFCs exhibited good linear relationships ranging from 1 to100 μg/L， with correlation coefficients （R2） ranging from 0.997 6 to 0.999 9. Limits of detection and quantification （LODs and LOQs， respectively） were determined to be 0.001–0.620 ng/L and 0.002–2.065 ng/L， respectively， indicative of high sensitivity. The 11 PFCs exhibited recoveries of 60.8%–120.0% at various concentrations （0.05， 1， 10， and 50 μg/L）. Relative standard deviations （RSDs） ranged from 1.0% to 20.0%， which meet the requirements for PFC analysis in water. The concentrations of the 11 PFCs at 15 sites in the Dongtiaoxi River， Hangzhou （near factories， reservoirs and residential areas） were analyzed using the developed method. A total of six PFCs， namely perfluorooctanoic acid （PFOA）， perfluorononanoic acid （PFNA）， perfluorooctane sulfonic acid （PFOS）， perfluoroheptanoic acid （PFHpS）， perfluorobutanesulfonate （PFBS） and perfluorodecanoic acid （PFDA）， were detected at mass concentrations of 11.4–30.7 ng/L. The highest mass concentration of PFOA was determined to be 25.5 ng/L. The PFCs in the Dongtiaoxi River were found to be mainly associated with precursor degradation and industrial wastewater discharge. A sudden rise in the pollution level was observed near the sampling point with the lowest detected concentration， which is possibly ascribable to the strong hydrodynamic difference between the hydraulic transport process near the river wharf and the highly turbulent flowing water. This difference results in the suspended particles in surface water mixing with re-suspended sediment particles such that PFCs are released back into the surface water. Pollution levels were observed to continuously decrease in the directions of the extended river and its estuary and tributaries. Risk assessments revealed that the PFC levels in the surface water of the Dongtiaoxi River basin are much lower than the official health reference value and have not reached levels that are expected to cause ecological harm and risk human health. The data are expected to support monitoring-system improvements by providing an in-depth understanding of occurrence characteristics， and help formulate a management plan for PFCs in the Dongtiaoxi River.

Key words: magnetic solid-phase extraction （MSPE）, ultra-high performance liquid chromatography-tandem mass spectrometry （UHPLC-MS/MS）, perfluorinated compounds （PFCs）, water

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