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.