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Per- and polyfluoroalkyl substances (PFAS), in the polymeric form, have been used extensively in functional textiles, including firefighter's turnout gear (e.g., jackets and pants), where PFAS are applied to confer oil and water resistance. However, growing concerns over the persistence, potential toxicity, and environmental impact of PFAS have prompted a thorough assessment of potential exposure pathways. Here, we report the emission of PFAS from three firefighter turnout gear jackets at 38 °C. Volatile emissions from the three layers (outer layer, moisture barrier, and thermal liner) were collected onto sorbent tubes via dynamic headspace sampling using a micro-scale chamber device kept at 38 °C for one hour. The emission was characterized using thermal desorption (TD) coupled to two-dimensional gas chromatography - time-of-flight mass spectrometry (GC×GC-TOF MS). The enhanced separation capacity of GC×GC was essential due to the high number of compounds present in each sample, especially for the fabrics from used turnout gear jackets. Based on the filtering expressions, including two-dimensional retention time ( 1 t r and 2 t r ) and PFAS diagnostic fragment ions (m/z 69, 95, and 131), fluorotelomer alcohols (FTOHs) and fluorotelomer acrylates were identified using standards and spectral matching with the NIST database. After conducting a non-targeted tile-based workflow, jackets (both used and unused) and layers were compared, resulting in the identification of the top 15 discriminating features from over 400 chromatographic peaks. Finally, preliminary FTOH emission experiments showed some usage and layers trends that are aligned with those reported using solvent extraction. Highest levels of FTOHs were found in the moisture barrier, followed by the outer layer and the thermal liner. Older jackets emitted higher levels of 8:2 FTOH and 10:2 FTOH than a newer jacket. In contrast, a newer jacket used for one year had emissions containing higher levels of 6:2 FTOH. Investigating routes of exposure and identifying new PFAS targets are critical steps in evaluating the environmental and health impacts of these persistent chemicals., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Laura McGregor reports a relationship with SepSolve Analytical Ltd that includes: employment. Matthew Edwards reports a relationship with SepSolve Analytical Ltd that includes: employment. Jonathan Grandy reports a relationship with SepSolve Analytical Ltd that includes: employment. Hannah Calder reports a relationship with Markes International Ltd that includes: employment. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Firefighters can be exposed to complex mixtures of airborne substances, including hazardous substances released during structural fires. This study employed silicone wristbands (SWBs) as passive samplers to investigate potential exposure to polycyclic aromatic hydrocarbons (PAHs) and flame retardants (FRs). SWBs were deployed at different areas of four fire stations, in four truck cabins, and at an office control location; they were also donned outside the jackets of 18 firefighters who responded to fire calls. Overall, office areas had significantly lower PAHs than fire station areas. Vehicle bays and truck cabins had significantly higher concentrations of low molecular weight (LMW) PAHs than sleeping and living room areas. For organophosphate ester flame retardants (OPFRs), tri-n-butyl phosphate (TnBP) and tris(1-chloro-2-propyl) phosphate (TCPP) were detected in all the samples; 2-ethylhexyl diphenyl phosphate (EHDPP) was more frequently detected in the fire station areas. Triphenyl phosphate (TPP) concentrations were highest in the truck cabin and office areas, and tris(1,3-dichloro-2-propyl)phosphate (TDCPP) was highest in truck cabins. Thirteen of 16 PAHs and nine of 36 OPFRs were detected in all the SWBs worn by firefighters, and tris (2-butoxyethyl) phosphate (TBEP) was the predominant OPFR. Levels of LMW PAHs were significantly lower when firefighters did not enter the fire. LMW PAHs, HMW (high molecular weight) PAHs, and EHDPP were significantly elevated when heavy smoke was reported. This work highlights the potential for occupational exposure to PAHs and flame retardants in some fire station areas; moreover, factors that may influence exposure during fire suppression. Whilst firefighters' occupational exposure to PAHs is likely related to fire suppression and exposure to contaminated gear and trucks, exposure to OPFRs may be more related to their presence in truck interiors and electronics.

Firefighters experience exposures to carcinogenic and mutagenic substances, including polycyclic aromatic hydrocarbons (PAHs). Silicone wristbands (SWBs) have been used as passive samplers to assess firefighters' exposures over the course of a shift but their utility in measuring short term exposures, source of exposure, and correlations with other measurements of exposure have not yet been investigated. In this study, SWBs were used to measure the concentrations of 16 priority PAHs inside and outside of firefighters' personal protective equipment (PPE) while firefighting. SWBs were placed on the wrist and jacket of 20 firefighters conducting live fire training. Correlations were made with matching data from a sister project that measured urinary concentrations of PAH metabolites and PAH concentrations from personal air samples from the same participants. Naphthalene, acenaphthylene and phenanthrene had the highest geometric mean concentrations in both jacket and wrist SWB, with 1040, 320, 180 ng/g SWB for jacket and 55.0, 4.9, and 6.0 ng/g SWB for wrist, respectively. Ratios of concentrations between the jacket and wrist SWBs were calculated as worker protection factors (WPFs) and averaged 40.1 for total PAHs and ranged from 2.8 to 214 for individual PAHs, similar to previous studies. Several significant correlations were observed between PAHs in jacket SWBs and air samples (e.g., total and low molecular weight PAHs, r = 0.55 and 0.59, p < 0.05, respectively). A few correlations were found between PAHs from SWBs worn on the wrist and jacket, and urinary concentrations of PAH metabolites and PAH concentrations in air samples. The ability of the SWBs to accurately capture exposures to various PAHs was likely influenced by short sampling time, high temperatures, and high turbulence. Future work should further examine the limitations of SWBs for PAH exposures in firefighting, and other extreme environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)