In-Vial Extraction Large Volume Gas Chromatography Mass Spectrometry for Analysis of Volatile PFASs on Papers and Textiles

Abstract

Volatile per- and polyfluorinated alkyl substances (PFASs) are found in consumer goods that contribute to human exposure to PFASs. Volatile PFAS precursors transform to perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) in both humans and the environment. Established methods for volatile PFASs in consumer goods exist, but higher sample throughput and greener sample preparation methods are needed to minimize analyte loss, while maintaining sensitivity. New analytical methodology was developed where a 1.5 × 1.5 cm piece of paper or textile is placed into an autosampler vial with solvent and mass-labeled internal standards, sonicated for 30 min, and directly injected without removal of material from the autosampler vial. Large volume injection (20 μL) gas chromatography mass spectrometry was applied for the quantification for 21 individual PFASs from five classes: fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (N-MeFASA, N-EtFASA), and fluorinated sulfonamidoethanols (N-MeFASE, N-EtFASE). Nontargeted analysis revealed additional C-C homologues of N-MeFASE and N-EtFASE, which accounted for 14-18% of the total volatile PFASs on three textiles. Overlooking short-chain (≤C) N-MeFASE, N-EtFASE, and long-chained (10:2-14:2) FTOHs on older textiles from the 1980s leads to an underestimation of human and environmental exposure to volatile PFAS.

Environmental Sources, Chemistry, Fate, and Transport of Per‐ and Polyfluoroalkyl Substances: State of the Science, Key Knowledge Gaps, and Recommendations Presented at the August 2019 SETAC Focus Topic Meeting

“…Commonly used HRMS instrumentation applied for aqueous and extractable PFAS includes LC/quadrupole-time of flight/ ion trap coupled to time-of-flight (QTOF/IT-TOF)-HRMS. Alternatively, to identify more volatile PFAS present in the samples, gas chromatography (GC) coupled to TOF-HRMS techniques can be applied (Rewerts et al, 2018). For example, GC-TOF-HRMS techniques are applicable to measure the volatiles generated as PICs during the thermal treatment of PFAS.…”

From Pesticides to Per- and Polyfluoroalkyl Substances: An Evaluation of Recent Targeted and Untargeted Mass Spectrometry Methods for Xenobiotics

“…Due to the large volume used, a comparable sensitivity to conventional methods was observed, and untargeted analysis revealed previously overlooked short-chain fluorinated sulfonamides. 53 To aid in the discovery of novel PFAS, Liu et al recently implemented an in-source fragmentation flagging scan in parallel with a high-resolution full scan to flag the retention times of PFAS ions based on their diagnostic fluorine-containing fragments. The flagged ions are then further investigated with a second MS/MS scan.…”

“…For the analysis of volatile PFAS on paper and textiles, Rewerts et al developed a novel high-throughput, low-waste sample preparation method prior to large volume GC-MS analysis. Due to the large volume used, a comparable sensitivity to conventional methods was observed, and untargeted analysis revealed previously overlooked short-chain fluorinated sulfonamides …”

Field Sampling Materials Unlikely Source of Contamination for Perfluoroalkyl and Polyfluoroalkyl Substances in Field Samples

“…Although there are numerous studies documenting concentrations of PFAS in consumer products (e.g., papers, textiles), − Denly et al was the first to quantify PFAS that leached into water over a 24 h period from materials including tubing, bailers, and water level tape measures, which come in direct contact with field samples. Materials also tested (e.g., food packaging, bubble wrap, plastic bags, sample labels, and field notebook parts) are unlikely to have direct contact with water or soil samples.…”