Zwitterionic, Cationic, and Anionic Fluorinated Chemicals in Aqueous Film Forming Foam Formulations and Groundwater from US Military Bases by Nonaqueous Large-Volume Injection HPLC-MS/MS
Zwitterionic, Cationic, and Anionic Fluorinated Chemicals in Aqueous Film Forming Foam Formulations and Groundwater from US Military Bases by Nonaqueous Large-Volume Injection HPLC-MS/MS
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DOI：
10.1021/es3034999
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发表时间：
2013-05-21
影响因子：
11.4
通讯作者：
Field, Jennifer A.
中科院分区：
文献类型：
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作者：
Backe, Will J.;Day, Thomas C.;Field, Jennifer A.
开发了一种新的分析方法，以量化地下水和水性成膜泡沫（AFFF）配方中的26种新发现的和21种遗留物质（如全氟烷基羧酸盐、全氟烷基磺酸盐和氟调聚物磺酸盐）。在分析之前，将AFFF制剂稀释到甲醇中，并对地下水中的PFAS进行微量液液萃取。通过大体积进样（900 μ L）高效液相色谱串联质谱法分析AFFF制剂和地下水提取物的甲醇稀释液。正交色谱法进行使用阳离子交换（二氧化硅）和阴离子交换（丙胺）保护柱串联F Tine反相（C18）分析柱。地下水中PFAS的方法检测限范围为0.71 ng/L至67 ng/L，对于匹配的真实分析标准品的分析物，整个方法的准确度范围为96%至106%。对于没有真实分析标准的分析物，整个方法的准确度范围为78%至144%，整个方法的精密度小于15%的相对标准偏差的所有分析物。对来自五个军事基地的地下水样本进行的方法演示显示，26种新发现的PFAS中有8种的浓度高达6900 ng/L。相对于传统的PFAS，新确定的PFAS代表了地下水中含氟化学品的一小部分。PFAS在地下水中的分布不同于基于氟调聚物和电氟化的AFFF制剂中发现的分布，这可能表明PFAS的环境转化。
A new analytical method was developed to quantify 26 newly-identified and 21 legacy (e.g. perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and fluorotelomer sulfonates) per and polyfluorinated alkyl substances (PFAS) in groundwater and aqueous film forming foam (AFFF) formulations. Prior to analysis, AFFF formulations were diluted into methanol and PFAS in groundwater were micro liquid-liquid extracted. Methanolic dilutions of AFFF formulations and groundwater extracts were analyzed by large-volume injection (900 mu L) high-performance liquid chromatography tandem mass spectrometry. Orthogonal chromatography was performed using cation exchange (silica) and anion exchange (propylamine) guard columns connected in series to F Tine a reverse-phase (C18) analytical column. Method detection limits for PFAS in groundwater ranged from 0.71 ng/L to 67 ng/L, and whole-method accuracy ranged from 96% to 106% for analytes for which matched authentic analytical standards were available. For analytes without authentic analytical standards, whole-method accuracy ranged from 78% to 144%, and whole-method precision was less than 15% relative standard deviation for all analytes. A demonstration of the method on groundwater samples from five military bases revealed eight of the 26 newly-identified PFAS present at concentrations up to 6900 ng/L. The newly-identified PFAS represent a minor fraction of the fluorinated chemicals in groundwater relative to legacy PFAS. The profiles of PFAS in groundwater differ from those found in fluorotelomer- and electrofluorination-based AFFF formulations, which potentially indicates environmental transformation of PFAS.