超高效液相色谱-串联质谱法测定农田环境介质中5种超短链全氟及多氟烷基化合物

Determination of Five Ultra-short Chain PFASs in Farmland Environmental Media by Ultra-high Performance Liquid Chromatography-tandem Mass Spectrometry

  • 摘要: 全氟及多氟烷基化合物(PFASs)因其广泛的环境持久性、生物累积性与潜在生态健康风险而备受关注, 而农田环境是这类污染物的重要汇与源。为科学评价农田环境安全, 本文建立了一种可同步测定稻田水与稻田土壤中5种超短链PFASs的分析方法。水样分别采用直接进样法与固相萃取法进行前处理, 土壤样品经甲醇提取后, 进一步采用固相萃取法净化; 采用超高效液相色谱-串联质谱(UPLC-MS/MS)仪, 在多反应离子监测模式(MRM)下对目标物进行检测, 定量方式采用内标法。结果表明, 5种超短链PFASs在各自设定的浓度范围内线性关系良好(R2≥0.998), 其中三氟乙酸(TFA)的线性范围为50~2 000 ng·L-1, 其余4种超短链PFASs的线性范围均为10~2 000 ng·L-1。方法回收率与精密度验证结果如下: 采用直接进样法处理水样时, 在60~200 ng·L-1加标水平下, 5种目标物的回收率为90.3%~105%, 相对标准偏差(RSD, n=6)为0.9%~3.6%;采用固相萃取法处理水样时, 在0.5~5 ng·L-1加标水平下, 回收率为75.6%~95.3%, RSD为1.0%~5.1%;土壤样品在20~200 ng·kg-1加标水平下, 5种目标物的回收率为74.2%~91.2%, RSD为1.2%~3.0%。5种目标物在本方法中的检出限为0.056~11 ng·L-1, 在水体与土壤基质中的定量限分别为0.5~60 ng·L-1和20 ng·kg-1。该方法操作简便、灵敏度高、重现性良好, 适用于农田环境介质中超短链PFASs的快速筛查与准确定量分析。

     

    Abstract: Per- and polyfluoroalkyl substances (PFASs) have drawn significant global concern due to their environmental persistence, bioaccumulation potential, and the associated ecological and health risks. Agricultural environment acts as critical sink and secondary source of these pollutants. To support the accurate assessment of farmland safety, this study established a robust analytical method for the simultaneous determination of five ultrashort-chain PFASs in paddy water and soil. Water samples were pretreated using both direct injection and solid-phase extraction (SPE), while soil samples were extracted with methanol followed by SPE cleanup. All extracts were analyzed by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) under multiple reaction monitoring (MRM) mode, with quantification performed via the internal standard method. The results demonstrate good linearity for the five target compounds over specified concentration ranges (TFA: 50-2 000 ng·L-1; other four ultrashort-chain PFASs: 10-2 000 ng·L-1), with correlation coefficients (R2) ≥ 0.998. For water samples processed by direct injection, recoveries ranged from 90.3% to 105% at spiked levels of 60-200 ng·L-1, with relative standard deviations (RSD, n=6) of 0.9%-3.6%. For the SPE method, recoveries were between 75.6% and 95.3% at spiking levels of 0.5-5 ng·L-1, with RSD of 1.0%-5.1%. In soil, recoveries ranged from 74.2% to 91.2% at spiked concentrations of 20-200 ng·kg-1, accompanied by RSD of 1.2%-3.0%. The method detection limits for the five analytes were between 0.056 and 11 ng·L-1, with quantification limits of 0.5-60 ng·L-1 in water and 20 ng·kg-1 in soil. This method is simple, sensitive, and reproducible, making it well-suited for the rapid screening and accurate quantification of ultrashort-chain PFASs in complex farmland matrices.

     

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