Abstract
Volatile per- and polyfluoroalkyl substances (PFASs) are often used as precursors in the synthesis of nonvolatile PFASs. The volatile PFASs, which include the perfluoroalkyl iodides (PFAIs), fluorotelomer iodides (FTIs), fluorotelomer alcohols (FTOHs), fluorotelomer olefins (FTOs), fluorotelomer acrylates (FTACs), and fluorotelomer methacrylates (FTMACs), are often produced starting from the telomerization process. These volatile compounds can be present in the air and water environment and can be transformed into highly persistent perfluoroalkyl carboxylic acids. With the exception of FTOHs, which are well studied, the determination of other volatile PFASs is also of prime importance in studying the sources and fate of PFASs. In this study, a method was developed to determine representative precursor compounds that included PFAIs, FTIs, FTOs, FTACs, and FTMACs in wastewater treatment plant (WWTP) air and water samples. The sampling and sample preparation step involved the use of solid-phase extraction (SPE) cartridges with HLB™ material to enrich the analyte. Gas chromatography with mass spectrometry was employed for the detection and quantification of the analytes. Method validation results showed high linearity and sensitivity in the positive electron ionization-selected ion monitoring mode (+EI-SIM). The absolute instrumental limits of detection were in the range of 0.5 to 2 pg. The method detection limit (MDL) in air was 1 ng/m3 with the exception of the FTACs which could be only be detected at concentrations higher than 40 ng/m3. The MDL in water was 10 ng/L. Direct spiking of the cartridges and analyte introduction by volatilization from the glass surface onto the SPE material had recoveries between 86 and 100%. The volatile PFASs were shown to readily partition into the air rather than into water. Consequently, large losses in the amount of PFASs were observed when these were spiked into the water.Graphical abstractWastewater treatment plant air and water samples were passed through HLB™ solid-phase materials. The eluates were injected onto a GC-MS system to simultaneously determine the volatile PFASs.
Highlights
The interest in determining the different poly- and perfluorinated alkyl substances (PFASs) in the environment has increased rapidly in recent years
We report on the development and validation of a complete method to determine the volatile PFASs except fluorotelomer alcohols (FTOHs) in industrial and municipal wastewater treatment plant (WWTP) air and water
We report on the difficulty we encountered in assessing the accuracy of the method for WWTP influents and effluents
Summary
The interest in determining the different poly- and perfluorinated alkyl substances (PFASs) in the environment has increased rapidly in recent years. Perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs), their C8 homologues perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), have been the subject of many studies—their occurrence, fate, and distribution in different samples and environmental compartments [1]; their biodegradability and bioaccumulation [2, 3]; and their toxicities to different organisms [4, 5] In controlling these substances, there is a need to identify their possible sources. The majority of PFASs are synthesized starting from the telomerization process (Fig. 1) It involves first, a UVcatalyzed radical reaction of trifluoromethyl iodide producing perfluoroalkyl iodides (PFAI) of varying number of carbon atoms [1, 9]. Monomers like acrylates and methacrylates are esterified with FTOHs producing fluorotelomer acrylates and methacrylates (FTACs and FTMACs)
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