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Application of High-Resolution Mass Spectrometry to Evaluate UV-Sulfite-Induced Transformations of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF)
Environmental Science & Technology ( IF 11.4 ) Pub Date : 2022-09-26 , DOI: 10.1021/acs.est.2c03228
Raul Tenorio 1, 2 , Andrew C Maizel 2, 3 , Charles E Schaefer 4 , Christopher P Higgins 2 , Timothy J Strathmann 2
Affiliation  

UV-sulfite has been shown to effectively degrade per- and polyfluoroalkyl substances (PFASs) in single-solute experiments. We recently reported treatment of 15 PFASs, including perfluoroalkyl sulfonic acids (PFSAs), perfluoroalkyl carboxylic acids (PFCAs), and fluorotelomer sulfonic acids (FTSs), detected in aqueous film-forming foam (AFFF) using high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Here, we extend the analysis within those original reaction solutions to include the wider set of PFASs in AFFF for which reactivity is largely unknown by applying recently established LC-QTOF-MS suspect screening and semiquantitative analysis protocols. Sixty-eight additional PFASs were detected (15 targeted + 68 suspect screening = 83 PFASs) with semiquantitative analysis, and their behavior was binned on the basis of (1) detection in untreated AFFF, (2) PFAS photogeneration, and (3) reactivity. These 68 structures account for an additional 20% of the total fluorine content in the AFFF (targeted + suspect screening = 57% of total fluorine content). Structure–reactivity trends were also revealed. During treatment, transformations of highly reactive structures containing sulfonamide (–SO2N–) and reduced sulfur groups (e.g., –S– and –SO–) adjacent to the perfluoroalkyl [F(CF2)n–] or fluorotelomer [F(CF2)n(CH2)2–] chain are likely sources of PFCA, PFSA, and FTS generation previously reported during the early stages of reactions. The results also show the character of headgroup moieties adjacent to the F(CF2)n–/F(CF2)n(CH2)2– chain (e.g., sulfur oxidation state, sulfonamide type, and carboxylic acids) and substitution along the F(CF2)n– chain (e.g., H–, ketone, and ether) together may determine chain length-dependent reactivity trends. The results highlight the importance of monitoring PFASs outside conventional targeted analytical methodologies.

中文翻译:

应用高分辨率质谱法评估紫外亚硫酸盐诱导的水成膜泡沫 (AFFF) 中全氟和多氟烷基物质 (PFAS) 的转化

在单溶质实验中,UV-亚硫酸盐已被证明可有效降解全氟烷基物质和多氟烷基物质 (PFAS)。我们最近报道了对 15 种 PFAS 的处理,包括全氟烷基磺酸 (PFSA)、全氟烷基羧酸 (PFCA) 和含氟调聚物磺酸 (FTS),使用高分辨率液相色谱四极杆时间-在水成膜泡沫 (AFFF) 中检测到飞行质谱 (LC-QTOF-MS) 靶向分析。在这里,我们通过应用最近建立的 LC-QTOF-MS 可疑筛选和半定量分析方案,将分析扩展到这些原始反应解决方案中,以包括 AFFF 中反应性在很大程度上未知的更广泛的 PFAS。通过半定量分析检测到另外 68 种 PFAS(15 种靶向 + 68 种可疑筛查 = 83 种 PFAS),并且它们的行为是基于(1)在未经处理的 AFFF 中检测,(2)PFAS 光生,和(3)反应性。这 68 种结构占 AFFF 中总氟含量的额外 20%(目标 + 可疑筛选 = 总氟含量的 57%)。还揭示了结构反应趋势。在治疗过程中,含有磺胺(-SO2 N–) 和与全氟烷基 [F(CF 2 ) n –] 或含氟调聚物 [F(CF 2 ) n (CH 2 ) 2 –] 链相邻的还原硫基团(例如 –S– 和 –SO–)是PFCA、PFSA 和 FTS 生成的可能来源以前报告过在反应的早期阶段。结果还显示了与 F(CF 2 ) n -/F(CF 2 ) n (CH 2 ) 2 - 链相邻的头基部分的特征(例如,硫氧化态、磺酰胺类型和羧酸)以及沿F(CF 2 ) n– 链(例如,H-、酮和醚)一起可以确定依赖于链长的反应趋势。结果强调了在常规目标分析方法之外监测 PFAS 的重要性。
更新日期:2022-09-26
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