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.

Polymeric textile materials, now, find extensive application in modern society than previously imagined, particularly in protective clothing. The application of these polymeric materials has been restricted by their flammability and contribution to fire risk. Flame retarding compounds and inherent flame-retardant materials have been introduced to reduce and even halt the flammability of polymers. However, over time, flame retardants tend to leach out of materials. The exposure of polymer textile to varying heat intensities may trigger polymer and flame retardant’s volatilization and thermal degradation. Firefighters may be exposed to toxic chemicals through the volatilization of flame-retardant compounds from the bunker gear. Flame retardant’s volatilization is associated with thermal degradation of the flame-retardant chemical compounds in the textile material. This review focuses on volatilization of flame retardants from protective textile materials resulting from exposure to heat and seeks to provide the necessary understanding about the release of flame retardants from flame-retardant textiles, particularly firefighting garments.