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.

Facemasks are important tools for fighting against disease spread, including Covid-19 and its variants, and some may be treated with per-and polyfluoroalkyl substances (PFAS). Nine facemasks over a range of prices were analyzed for total fluorine and PFAS. The PFAS compositions of the masks were then used to estimate exposure and the mass of PFAS discharged to landfill leachate. Fluorine from PFAS accounted only for a small fraction of total fluorine. Homologous series of linear perfluoroalkyl carboxylates and the 6:2 fluorotelomer alcohol indicated a fluorotelomer origin. Inhalation was estimated to be the dominant exposure route (40%−50%), followed by incidental ingestion (15%− 40%) and dermal (11%−20%). Exposure and risk estimates were higher for children than adults, and high physical activity substantially increased inhalation exposure. These preliminary findings indicate that wearing masks treated with high levels of PFAS for extended periods of time can be a notable source of exposure and have the potential to pose a health risk. Despite modeled annual disposal of ∼29−91 billion masks, and an assuming 100% leaching of individual PFAS into landfill leachate, mask disposal would contribute only an additional 6% of annual PFAS mass loads and less than 11 kg of PFAS discharged to U.S. wastewater.

Paints are widely used in indoor settings yet there are no data for volatile per-and polyfluoroalkyl substances (PFAS) for paints or knowledge if paints are potentially important sources of human exposure to PFAS. Different commercial paints (n = 27) were collected from local hardware stores and analyzed for volatile PFAS by gas chromatography−mass spectrometry (GC−MS), nonvolatile PFAS by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-qTOF), and total fluorine by 19 F nuclear magnetic resonance spectroscopy (NMR). Diluted paint required clean up to remove 6:2 fluorotelomer phosphate diester (diPAP), which thermally transforms into 6:2 FTOH at 280 °C (GC inlet temperature). Only 6:2 FTOH (0.9−83 μg/g) and 6:2 diPAP (0.073−58 μg/g) were found in five exterior and nine interior paints and only accounted for a maximum of 17% of total fluorine. Upon drying, 40% of the FTOH mass was lost, and the loss was verified by measurements of the cumulative FTOH mass measured in the air of a small, confined space over a 3 h period. Based on the liquid paint results, the ConsExpo model was used for potential exposure assessment and one commercial paint exceeded the chosen reference dose (5 μg/kg-day) for children and adults, indicating the potential for human exposure during painting.

Semiquantitation of suspect per-and polyfluoroalkyl substances (PFAS) in complex mixtures is challenging due to the increasing number of suspect PFAS. Traditional 1:1 matching strategies require selecting calibrants (target−surrogate standard pairs) based on head group, fluorinated chain length, and retention time, which is time-consuming and requires expert knowledge. Lack of uniformity in calibrant selection for estimating suspect concentrations among different laboratories makes comparing reported suspect concentrations difficult. In this study, a practical approach whereby the area counts for 50 anionic and 5 zwitterionic/cationic target PFAS were ratioed to the average area of their respective stable-isotope labeled surrogates to create "average PFAS calibration curves" for suspects detected in negative-and positive-ionization mode liquid chromatography quadrupole time-of-flight mass spectrometry. The calibration curves were fitted with log−log and weighted linear regression models. The two models were evaluated for their accuracy and prediction interval in predicting the target PFAS concentrations. The average PFAS calibration curves were then used to estimate the suspect PFAS concentration in a well-characterized aqueous film-forming foam. Weighted linear regression resulted in more target PFAS that fell within 70−130% of their known standard value and narrower prediction intervals than the log−log transformation approach. The summed suspect PFAS concentrations calculated by weighted linear regression and log−log transformation were within 8 and 16% of those estimated by a 1:1 matching strategy. The average PFAS calibration curve can be easily expanded and can be applied to any suspect PFAS even if the confidence in the suspect structure is low or unknown.

Exposures to per- and polyfluoroalkyl substances (PFAS) are of increasing concern. Assessments typically focus only on ingestion and inhalation exposure due to a lack of generally accepted approaches for estimating dermal absorption. Prior work indicates limited dermal absorption of ionic PFAS, but absorption of neutral PFAS has not been examined from the liquid vehicle or from vapor. Partitioning of semivolatile organic compounds from the gas phase to the skin surface (i.e., stratum corneum) is well known, but the potential for partitioning of neutral PFAS from the gas phase to the stratum corneum has yet to be estimated. The SPARC-estimated physicochemical properties were used to calculate transdermal permeability coefficients (k p_g) and dermal-to-inhalation (D/I) exposure ratios for two groups of neutral PFAS, including those on a U.S. Environmental Protection Agency PFAS list. 11 neutral PFAS gave calculated D/I ratios >5, indicating that direct transdermal absorption may be an important exposure pathway compared to inhalation. Data on consumer products or indoor air is needed for the 11 neutral PFAS, followed by possible biomonitoring to experimentally verify dermal absorption from air. Additional PFAS should be estimated by the protocol used here as they are identified in commercial products.

This work was in response to the Defense Logistic Agency’s (DLA) Subsistence Network Broad Agency Announcement, BAA-0003-16 addressing 2019 NDAA Section 329 that states packaging materials used for Meals Ready-to-Eat (MRE) that contact food products must be free of per- and polyfluoroalkyl substances (PFAS). This was addressed by determining the presence or absence of PFAS on MREs by extraction followed by gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS). Any samples positive for PFAS were quantitated using LC triple quadrupole (QqQ) MS at the US Army Engineering and Research Development Center (ERDC) and by high resolution quadrupole time-of-flight (qTOF) MS and GC-MS at Oregon State University (OSU).

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