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多孔芳香骨架涂层搅拌棒吸附萃取结合气相色谱法分析大气颗粒物和环境水样中的 16 种多环芳烃。

Porous aromatic framework coated stir bar sorptive extraction coupled with gas chromatography for the analysis of 16 polycyclic aromatic hydrocarbons in atmospheric particles and environmental water samples.

机构信息

Department of Chemistry, Wuhan University, Wuhan, 430072, China.

Hubei Key Laboratory of Environmental and Health Effects of Persistent Toxic Substances, School of Environment and Health, Jianghan University, Wuhan, 430056, China.

出版信息

J Chromatogr A. 2022 Jun 21;1673:463139. doi: 10.1016/j.chroma.2022.463139. Epub 2022 May 11.

Abstract

In this work, porous aromatic frameworks (PAFs) with different pore size were evaluated for simultaneous adsorption of 16 polycyclic aromatic hydrocarbons (PAHs) with large difference in polarity and molecular size. Two other porous organic polymers containing electron pushing/withdrawing group were investigated along for a comparison, and PAF-120 with the pore size of appr. 2.1 nm exhibited the highest extraction efficiency. Based on water contact angle and molecular dynamics simulation, the adsorption of 16 PAHs on PAF-120 was attributed to hydrophobic interaction, π-π interaction and molecular sieving effect. PAF-120/PDMS coated stir bar was then prepared by physical adhesion, and a method of stir bar sorptive extraction-gas chromatography-flame ionization detector was established for trace PAHs analysis in environmental samples. Under the optimal experimental conditions, the limits of detection (S/N = 3) for 16 PAHs were found to be in the range of 42-375 ng/L, with the relative standard deviations of 4.1-14.6% (n = 7). The enrichment factors varied from 31 (Indeno[1,2,3-cd]pyrene) to 80-fold (anthracene), with the maximal enrichment factor of 100-fold. The proposed method was applied to the analysis of PAHs in local environmental water and atmospheric particle samples. None of the 16 PAHs were detected in the collected water samples. While for the collected atmospheric particles, 12 PAHs were detected in fine particulate matter (PM) within the range of 0.6-2.8 ng/m. For inhalable particulate matter (PM) and total suspended particulate matter (TSP), 16 PAHs were all detected in the range of 0.6-3.8 ng/m and 0.6-5.9 ng/m, respectively. Quantitative recoveries were obtained in recovery test, demonstrating the accuracy and application potential of the proposed method.

摘要

在这项工作中,评估了具有不同孔径的多孔芳香骨架(PAFs),以同时吸附极性和分子尺寸差异较大的 16 种多环芳烃(PAHs)。还研究了另外两种含有推拉电子基团的多孔有机聚合物作为对比,其中孔径约为 2.1nm 的 PAF-120 表现出最高的萃取效率。基于水接触角和分子动力学模拟,将 16 种 PAHs 吸附在 PAF-120 上归因于疏水相互作用、π-π相互作用和分子筛效应。然后通过物理吸附制备了 PAF-120/PDMS 涂层搅拌棒,并建立了搅拌棒吸附萃取-气相色谱-火焰离子化检测器法用于环境样品中痕量 PAHs 的分析。在最佳实验条件下,发现 16 种 PAHs 的检出限(S/N=3)在 42-375ng/L 范围内,相对标准偏差为 4.1-14.6%(n=7)。富集因子范围为 31(茚并[1,2,3-cd]芘)至 80 倍(蒽),最大富集因子为 100 倍。该方法用于分析当地环境水样和大气颗粒物样品中的 PAHs。在所采集的水样中均未检测到 16 种 PAHs。而在所采集的大气颗粒物中,在细颗粒物(PM)中检测到 12 种 PAHs,浓度范围为 0.6-2.8ng/m。在可吸入颗粒物(PM)和总悬浮颗粒物(TSP)中,均检测到 16 种 PAHs,浓度范围分别为 0.6-3.8ng/m 和 0.6-5.9ng/m。在回收试验中获得了定量回收率,证明了该方法的准确性和应用潜力。

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