Metal-Organic Frameworks for the Trace Multiplexed Quantitation of 50 PFAS by Liquid Chromatography Mass Spectrometry

William, Donald, Lisa, Hua, Marcello, Solomon, Deanna, D'Alessandro
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Abstract

Per- and polyfluoroalkyl substances (PFAS) are environmental contaminants of increasing concern due to their persistence and potential health impacts. New guidelines with exceedingly low detection limits necessitate the development of promising materials for preconcentration. Six different metal-organic frameworks were evaluated for their potential as dispersive solid-phase extraction (dSPE) sorbents for PFAS quantitation by quantitative liquid chromatography tandem mass spectrometry (LC-MS/MS). UiO-66 demonstrated the highest combined average adsorption (87%) and recovery (85%) across 33 PFAS spiked in water at 2 ppb, and 75% recovery for 50 PFAS at 200 ppq. The developed dSPE workflow using UiO-66 resulted in limit of detections (LODs) as low as 4 ppq with average LODs of 108 ppq across 50 PFAS by testing at concentrations of 200 to 800 ppq. UiO-66 retained its crystalline structure post-PFAS adsorption, indicating stability for dSPE. Nearly 100% average recovery across all 50 PFAS was observed for UiO-66 using a 20 ppt spike, whereas ZIF-8 resulted in lower recovery. The efficacy of using UiO-66 as a dSPE material was assessed using six environmental water samples from different locations in Sydney, Australia, with all samples having quantifiable levels of PFAS. In water collected from Sydney Airport, 22 PFAS were detected above the limit of quantification (LOQ). Across all environmental water samples, a total of 25 PFAS were quantified above LOQs, with internal standard recoveries between 70-120%. In addition, the presence of multiply charged counterions decreased short-chained PFAS adsorption, while chloride had no impact. While polymeric resins have been used for screening ~50 PFAS with limits of detection ranging from 1 to 80 ppt, UiO-66 can be used to detect 50 PFAS at concentrations as low as 200 ppq. The high performance of UiO-66 in terms of recovery and detection limits underscores its potential for practical analytical applications in PFAS detection.
通过液相色谱质谱法对 50 种全氟辛烷磺酸进行痕量多重定量的金属有机框架
全氟和多氟烷基物质(PFAS)是一种环境污染物,由于其持久性和对健康的潜在影响而日益受到关注。新准则规定了极低的检测限,因此有必要开发有前景的预浓缩材料。我们评估了六种不同的金属有机框架作为分散固相萃取(dSPE)吸附剂的潜力,以便通过液相色谱串联质谱法(LC-MS/MS)对 PFAS 进行定量。UiO-66 对水中添加的 33 种 PFAS(浓度为 2 ppb)具有最高的综合平均吸附率(87%)和回收率(85%),对浓度为 200 ppq 的 50 种 PFAS 具有 75% 的回收率。使用 UiO-66 开发的 dSPE 工作流程通过对浓度为 200 至 800 ppq 的 50 种 PFAS 进行检测,检测限 (LOD) 低至 4 ppq,平均检测限为 108 ppq。UiO-66 在吸附 PFAS 后仍保持其晶体结构,这表明它对 dSPE 具有稳定性。使用 20 ppt 的尖峰浓度,UiO-66 对所有 50 种 PFAS 的平均回收率接近 100%,而 ZIF-8 的回收率较低。将 UiO-66 用作 dSPE 材料的功效是通过澳大利亚悉尼不同地点的六个环境水样进行评估的,所有水样中的 PFAS 含量均可量化。在悉尼机场采集的水样中,检测到 22 种 PFAS 超过了定量限 (LOQ)。在所有环境水样中,共有 25 种 PFAS 的定量超过了 LOQ,内标回收率在 70-120% 之间。此外,多电荷反离子的存在降低了对短链 PFAS 的吸附,而氯化物则没有影响。聚合树脂可用于筛选约 50 种 PFAS,检测限为 1 至 80 ppt,而 UiO-66 可用于检测浓度低至 200 ppq 的 50 种 PFAS。UiO-66 在回收率和检测限方面的高性能突显了其在 PFAS 检测的实际分析应用中的潜力。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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