Firefighting bunker gear is manufactured from flame-retardant materials, which resist ignition and delay flame spread. However, concerns have been emerging on the potential harmful effects of some flame retardants (FRs) commonly used in flame-retarding materials, particularly the brominated flame retardants. This study investigated the presence of flame retardants in bunker gear, particularly polybrominated diphenyl ethers and their congeners in the garments, and evaluated their impact on thermal performance. X-ray fluorescence spectroscopy was used to ascertain the presence of bromine as a possible indicator for brominated flame retardants. X-ray fluorescence results indicated the presence of Br in all samples, ranging from 444 to 20,367 µg/g. Further analysis via gas chromatography–mass spectrometry was done on samples. Brominated flame retardants, particularly polybrominated diphenyl ethers and hexabromocyclododecane, were detected in all samples with concentrations ranging from 261.61 to 1001.77 µg/g and 0.01 to 0.07 µg/g, respectively. The cone calorimeter was used, with 50 and 75 kW/m2 heat fluxes, to investigate the impact of the brominated flame-retardant concentrations, if any, on thermal performance. New bunker garments, particularly those with lower Br and brominated flame-retardant concentrations, were observed to have higher thermal performance.
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