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This work characterizes levels of eighteen polycyclic aromatic hydrocarbons (PAHs) in the breathing air zone of firefighters during their regular work shift at eight Portuguese fire stations, and the firefighters’ total internal dose by six urinary monohydroxyl metabolites (OH-PAHs). Total PAHs (ΣPAHs) concentrations varied widely (46.4–428 ng/m 3 ), mainly due to site specificity (urban/rural) and characteristics (age and layout) of buildings. Airborne PAHs with 2–3 rings were the most abundant (63.9–95.7% ΣPAHs). Similarly, urinary 1-hydroxynaphthalene and 1-hydroxyacenaphthene were the predominant metabolites (66–96% ΣOH-PAHs). Naphthalene contributed the most to carcinogenic ΣPAHs (39.4–78.1%) in majority of firehouses; benzo[a]pyrene, the marker of carcinogenic PAHs, accounted with 1.5–10%. Statistically positive significant correlations (r ≥ 0.733, p ≤ 0.025) were observed between ΣPAHs and urinary ΣOH-PAHs for firefighters of four fire stations suggesting that, at these sites, indoor air was their major exposure source of PAHs. Firefighter’s personal exposure to PAHs at Portuguese fire stations were well below the existent occupational exposure limits. Also, the quantified concentrations of post-shift urinary 1-hydroxypyrene in all firefighters were clearly lower than the benchmark level (0.5 μmol/mol) recommended by the American Conference of Governmental Industrial Hygienists. [ABSTRACT FROM AUTHOR]

• Urinary PAH metabolites and genotoxic/oxidative effects were assessed in firefighters. • Levels of total PAH metabolites were increased up to 340% in exposed subjects. • Urinary 1OHNaph+1OHAce, and 2OHFlu were the compounds with the highest increments. • Firefighting and tobacco smoke raised the oxidative DNA damage in exposed subjects. • Cardiac frequency, PAH metabolites and DNA damage can be used for health surveillance. Firefighters represent one of the riskiest occupations, yet due to the logistic reasons, the respective exposure assessment is one of the most challenging. Thus, this work assessed the impact of firefighting activities on levels of urinary monohydroxyl-polycyclic aromatic hydrocarbons (OHPAHs; 1-hydroxynaphthalene, 1-hydroxyacenaphthene, 2-hydroxyfluorene, 1-hydroxyphenanthrene, 1-hydroxypyrene, 3-hydroxybenzo(a)pyrene) and genotoxic/oxidative-effect biomarkers (basal DNA and oxidative DNA damage) of firefighters from eight firehouses. Cardiac frequency, blood pressure and arterial oxygen saturation were also monitored. OHPAHs were determined by liquid-chromatography with fluorescence detection, while genotoxic/oxidative-effect biomarkers were assessed by the comet assay. Concentrations of total OHPAHs were up to 340% higher (p ≤ 0.05) in (non-smoking and smoking) exposed workers than in control subjects (non-smoking and non-exposed to combat activities); the highest increments were observed for 1-hydroxynaphthalene and 1-hydroxyacenaphthene (82–88% of ∑OHPAHs), and for 2-hydroxyfluorene (5–15%). Levels of biomarker for oxidative stress were increased in non-smoking exposed workers than in control group (316%; p ≤ 0.001); inconclusive results were found for DNA damage. Positive correlations were found between the cardiac frequency, ∑OHPAHs and the oxidative DNA damage of non-smoking (non-exposed and exposed) firefighters. Evidences were raised regarding the simultaneous use of these biomarkers for the surveillance of firefighters' health and to better estimate the potential short-term health risks. [ABSTRACT FROM AUTHOR]