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AbstractThe combustion of petroleum-based fossil fuels is associated with a high environmental burden. Several alternative fuels, including synthetic fuels (e.g., gas-to-liquid, GTL) and biofuels (e.g., rapeseed methyl ester, RME) have been studied in the last few years. While the advantages for the environment (sustainability of biofuels) are well known, research on the resulting health effects from combustion aerosols of these alternative fuels is still scarce. Consequently, we investigated the chemical combustion profile from three distinct fuel types, including a petroleum-based fossil fuel (B0) and two alternative fuels (GTL, RME) under real exposure conditions. We sampled particulate matter (PM2.5, PM0.25) and the gas phase from heavy-duty machinery and evaluated the general pattern of volatile and semi-volatile organic compounds, elemental and organic carbon as well as a range of transition metals in the size segregated PM and/or gas phase. The use of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry enabled us to classify distinct methylated PAHs in the PM samples and its high abundance, especially in the fine fraction of PM. We found that (methylated) PAHs were highly abundant in the PM of B0 compared to GTL and RME. Highest concentrations of targeted aromatic species in the gas phase were released from B0. In summary, we demonstrated that GTL and RME combustion released lower amounts of chemical compounds related to adverse health effects, thus, the substitution of petroleum-based fuels could improve air quality for human and the environment.