Graham F. Peaslee

Firefighters have previously received attention for their occupational exposure to numerous chemicals of concern through their turnout gear, aqueous film-forming foam, and fire events. However, their station wear, uniforms worn daily in the station, has not yet been investigated for textile additives of concern. In this study, 57 firefighter station wear uniforms were screened using the paired method of particle-induced gamma-ray emission (PIGE) and particle-induced X-ray emission (PIXE) spectroscopies to estimate concentrations of 21 elements between F and Pb. As this is the first instance of quantifying elements in textiles using PIXE, validation of PIXE results was conducted using inductively coupled plasma–optical emission spectroscopy (ICP-OES), ultrahigh-performance liquid chromatography coupled to high-resolution tandem mass spectrometry (UHPLC-HRMS/MS), and gas chromatography–tandem mass spectrometry (GC-MS/MS). These analyses detected elevated concentrations of Cl, Zn, Cr, and/or Sb in numerous station-wear samples. Additionally, targeted liquid chromatography–tandem mass spectrometry (LC-MS/MS) for 31 per- and polyfluoroalkyl substances (PFAS) was performed on a subset of samples. Together, these results demonstrate the effectiveness of PIGE/PIXE for screening textiles and highlight the concerning presence of PFAS, flame retardants, and halogenated azobenzene disperse dyes in some station-wear uniforms.

Extensive use of per- and polyfluoroalkyl substances (PFAS) has led to their widespread contamination of the Great Lakes. Due to their resilient carbon-fluorine bonds, some PFAS bioaccumulate, biomagnify, and cause toxic effects in biota. In wild-caught Lake Michigan salmonids, perfluorooctane sulfonate (PFOS) concentrations were higher in eggs than in muscle tissue, suggesting maternal offloading. We evaluated PFOS exposure effects through egg development in rainbow trout, an introduced salmonid now important to the Great Lakes. We simulated maternal offloading of PFOS in vitro (0, 0.03, 0.3, 3, and 30 ppm) based on previous literature. Eggs were exposed for three hours, fertilized, and incubated until hatching to alevins. Samples were taken at various timepoints from egg to alevin and assessed for key markers of oxidative stress: lipid peroxidation, superoxide dismutase (SOD) activity and glutathione (GSH) abundance. PFOS accumulation in eggs was also analyzed at various development stages. At time zero, internal PFOS concentrations in eggs ranged from 1.02–44.1% of exposure solution concentrations, declining further through development. Oxidative stress indicators fluctuated through development. Lipid peroxidation levels generally decreased throughout treatments in alevins, with no significant difference observed in embryos. SOD activity varied throughout development; notably, embryo SOD levels in the 0.3 ppm treatment were lower than control at week four. GSH levels were above control in embryos at week four and generally fell below control in alevins. Overall, markers of oxidative stress showed varying trends (positive/negative) in eggs exposed to PFOS, which raises concerns for fish embryonic development and broader environmental impacts.

We read with interest the submission “Tissue Bioconcentration Pattern and Biotransformation of Per-Fluorooctanoic Acid (PFOA) in Cyprinus carpio (European Carp)—An Extensive In Vivo Study” by Petre et al

Northern Lake County, Indiana, United States, is a heavily industrialized area, containing steel mills, oil refineries, and chemical manufacturers surrounded by extensive residential neighborhoods. As part of an ongoing community-academic partnership to address environmental contamination in this area, road sediment was selected as a sample medium which is abundant, simple, and cost-effective. Elemental analysis of road sediment can provide a short-term history of atmospheric deposition of pollutants of interest. In this study, 387 road sediment samples were collected from 332 sampling sites in Northern Lake County across two years. The samples underwent particle-induced x-ray emission and gamma-ray emission spectroscopy at the University of Notre Dame to quantify up to 24 elements in each sample. Empirical Bayesian Kriging geospatial analysis and Positive Matrix Factorization were completed to identify potential contamination hotspots and sources. Empirical Bayesian Kriging results showed high geoaccumulation indices and heavy contamination factors for elements linked to areas of ongoing industrial activity in the region, particularly along the Lake Michigan coastline. Positive Matrix Factorization showed source contributions linked geospatially to regions of heavy industrial activity, which was further supported by corresponding individual correlations between elements of interest. The combination of road dust elemental analysis and geospatial techniques helped to better illustrate the contamination landscape of Northern Lake County and inform community members about predicted regional hotspots. Future work will compare these “background” elemental concentrations outdoors to those measured from interior house dust collected in this region, to identify potential pathways for personal exposure.

To understand if exterior building products are a source of perfluoroalkyl and polyfluoroalkyl substances (PFAS) to the environment, we measured PFAS in 145 samples of paints, sealers, and textiles, mostly intended for exterior use. We first developed a combined one and two-dimensional diffusion-ordered spectroscopy (1D and 2D-DOSY) fluorine nuclear magnetic resonance (¹⁹F NMR) method to characterize and quantify side-chain fluorinated polymers (SCFPs) and nonpolymeric PFAS. Results showed that 36% (22/61), 24% (13/54), and 70% (21/30) of tested paints, sealers, and textiles contained total organic fluorine (TOF) at 0.1-16.1, 0.4-2488, and 0.34-74.0 μmol/g, respectively. Paints mainly contained 6:2 fluorotelomer (FT) and aromatic-CF₃ nonpolymeric PFAS, while sealers also contained 6:2 FT SCFPs and perfluorobutane sulfonyl fluoride (PBSF)-based PFAS. Textiles contained 6:2 FT, 8:2 FT, and PBSF-based PFAS indicative of SCFPs. Advanced mass spectrometry methods revealed that paints and sealers with 6:2 FT nonpolymers mainly contained 6:2 fluorotelomer phosphate mono-, di-, and triesters (6:2 mono-, di-, and triPAPs) and 6:2 FT dipyrophosphate, while textiles primarily contained n:2 fluorotelomer alcohols (n:2 FTOH, n = 6, 8) or N-methyl perfluorobutane sulfonamide alcohol (MeFBSE). Based on the PFAS found in these products and the recommendation to reapply the coatings to protect exterior/interior surfaces and the replacement of exterior textiles, these results indicate that building products likely contribute polymeric and nonpolymeric PFAS to the environment.

The chemical properties of perfluoroalkyl and polyfluoroalkyl substances (PFAS) pose a significant remediation challenge. This study investigated smoldering combustion to destroy PFAS while scaling up from the lab to field implementation. The first phase consisted of bench-scale tests using a model soil system. Calcium oxide (CaO) was used as a soil amendment in some of the test cases. For all test conditions, greater than 99.9% removal of PFAS was achieved. Post-treatment soils without CaO amendments were found to have a significant reduction in total fluorine concentrations, while the fluorine concentrations in soils with CaO amendments were similar following treatment. This suggests that fluorine emissions from smoldering treatment of PFAS are captured by the presence of the calcium ion (Ca2+). Using new analytical methods, we better characterized the mass balance of the system. These lab results were carried out in a pilot study using soils from a PFAS-impacted site. Two large-scale tests treating 10 m3 of soil were completed. Results of the large-scale smoldering tests agreed with the results from the lab phase. The results from both phases provide a greater understanding of the fate of PFAS when it is treated by smoldering and detail the first large-scale demonstration of smoldering treatment for PFAS-impacted soils.

This report provides an overview of the current state of scientific knowledge concerning PFAS, as well as a concise assessment of current and potential impacts of its continued use. It discusses exposure pathways impacting the health of the people, organisms and environment in Indiana and the region. Also included are recommendations regarding pressing challenges and how individuals can work to reduce the presence of PFAS while also limiting exposure and negative impacts.