Disposition of Fluorine on New Firefighter Turnout Gear

Abstract

Firefighter turnout gear is essential for reducing occupational exposure to hazardous chemicals during training and fire events. Per-and polyfluoroalkyl substances (PFASs) are observed in firefighter serum, and possible occupational sources include the air and dust of fires, aqueous film-forming foam, and turnout gear. Limited data exist for nonvolatile and volatile PFASs on firefighter turnout gear and the disposition of fluorine on the individual layers of turnout gear. Further implications for exposure to fluorine on turnout gear are not well understood. Three unused turnout garments purchased in 2019 and one purchased in 2008, were analyzed for 50 nonvolatile and 15 volatile PFASs by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-qTOF-MS) and gas chromatography–mass spectrometry (GC–MS), respectively. Particle-induced gamma ray emission (PIGE), a surface technique, and instrumental neutron activation analysis (INAA), a bulk technique, were used to measure total fluorine. Bulk characterization of the layers by pyrolysis-GC/MS (py-GC/MS) was used to differentiate fluoropolymer (e.g., PTFE) films from textile layers finished with side-chain polymers. The outer layer, moisture barrier, and thermal layers of the turnout gear all yielded measured concentrations of volatile PFASs that exceeded nonvolatile PFAS concentrations, but the summed molar concentrations made up only a small fraction of total fluorine (0.0016–6.7%). Moisture barrier layers comprised a PTFE film, as determined by py-GC–MS, and gave the highest individual nonvolatile (0.159 mg F/kg) and volatile PFAS (20.7 mg F/kg) as well as total fluorine (122,000 mg F/kg) concentrations. Outer and thermal layers comprised aromatic polyamide-based fibers (aramid) treated with side-chain fluoropolymers and had lower levels of individual nonvolatile and volatile PFASs. Equal concentrations of total fluorine by both PIGE and INAA on the outer and thermal layers is consistent with treatment with a side-chain fluoropolymer coating. New turnout gear should be examined as a potential source of firefighter occupational exposure to nonvolatile and volatile PFASs in future assessments.

Per- and Polyfluoroalkyl Substances (PFAS) in Facemasks: Potential Source of Human Exposure to PFAS with Implications for Disposal to Landfills

“…Total fluorine in this study was among the highest measured in consumer products including textiles, papers, cosmetics, and food packaging. ,− No correlation was observed between the price of facemasks and total fluorine, total fluorine and PFAS, or the price of facemasks and PFAS. The contribution of PFAS to total fluorine was insignificant (Table ) and consistent with other measurements for textiles. , The gap in fluorine between total fluorine and PFAS from facemask to facemask is likely due to the presence of fluoropolymers, such as side-chain fluoropolymers, in some of these facemasks.…”

“…Facemasks are designed to not only prevent inhalation of particles or pathogens but also to repel fluids (e.g., bodily) . The repellency factor indicates the potential presence of per- and polyfluoroalkyl substances (PFAS), which are known components of specialty, water-repellant fabrics, such as firefighter turnout gear, jackets, − and surgical gowns . While there are numerous reports of PFAS in consumer products, − except for a news story on unnamed PFAS and a cross-linker used in textile treated with PFAS in facemasks, there is no published information on the presence of PFAS in facemasks.…”

Widespread Occurrence of Non-Extractable Fluorine in Artificial Turfs from Stockholm, Sweden

“…However, we cannot rule out contributions from inorganic fluorine species other than fluoride that may occur in the turf that could not be extracted in water. Ultra-short chain PFAS (possibly deposited via precipitation − ) or non-PFAA-forming organofluorine residuals (such as those detected in other fluoropolymer-containing products) may also contribute to the unidentified EOF observed in some samples. However, considering that EOF concentrations were typically more than 2 orders of magnitude lower than TF concentrations, substances making up the EOF appear to be relatively minor.…”

Neutral Per- and Polyfluoroalkyl Substances, Butyl Carbitol, and Organic Corrosion Inhibitors in Aqueous Film-Forming Foams: Implications for Vapor Intrusion and the Environment

“…All diluted samples were directly injected onto GC–MS without any cleanup. Neutral PFAS and organic corrosion inhibitors were analyzed in positive chemical ionization mode, , while BC was analyzed in electron impact mode. − Formation of mass-to-charge ( m / z ) ions in the MS, due to chemical ionization process, which corresponded to the same m / z ions of neutral PFAS, was taken into account in the calibration curve. Carryover of neutral PFAS following GC injection was not observed.…”

“…The term “neutral” per- and polyfluoroalkyl substance (PFAS) is used herein, instead of “volatile PFAS”, − and includes PFAS not expected to be charged at environmentally relevant pH and to avoid confusion with the term “volatile” in the context of vapor intrusion (VI). Neutral PFAS can be derived either from fluorotelomerization (FT) (e.g., fluorotelomer alcohols or FTOHs) or from electrochemical fluorination (ECF) (e.g., N -methyl- and N -ethyl perfluorooctane sulfonamides (MeFOSA and EtFOSA, respectively) and N -methyl- and N -ethyl perfluorooctane sulfonamido ethanols (MeFOSE and EtFOSE, respectively)).…”