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This work aims to characterize personal exposure of firefighters to polycyclic aromatic hydrocarbons (PAHs) in non-fire work environments (fire stations), and assesses the respective risks. Eighteen PAHs (16 considered by USEPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were monitored in breathing zones of workers at five Portuguese fire stations during a normal shift. The obtained levels of PAHs fulfilled all existent occupational exposure limits as well as air quality guidelines with total concentrations (ΣPAHs) in range of 46.8–155 ng m^− 3. Light compounds (2–3 rings) were the most predominant congeners (74–96% of ΣPAHs) whereas PAHs with 5–6 rings accounted 3–9% of ΣPAHs. Fuel and biomass combustions, vehicular traffic emissions, and use of lubricant oils were identified as the main sources of PAHs exposure at the studied fire corporations. Incremental lifetime cancer risks …