The fuel impact on the emission of more than 40 particulate associated polycyclic aromatic hydrocarbons (PAHs) in the molecular weight range 178-302 Da were investigated. The fuels; neat diesel (EN 590), rape seed methyl ester (B100) and a 30% w/w blend thereof (B30) were tested on a portable power generator without any exhaust aftertreatment. Gaseous emissions of carbon monoxide (CO), hydrocarbons (HC) and nitrogen oxides (NOx) were measured along with particulate emissions and its size distribution for the different fuels. Collected diesel particles were extracted using pressurized fluid extraction and analyzed using an online hyphenated liquid chromatography-gas chromatography-mass spectrometry system. The neat B100 and the B30 fuel produced less CO and total PAHs while the emissions of NOx and particulate matter increased compared with petroleum diesel fuel per kW h. The reduction of PAH emissions of the alternative diesel fuels were 36% and 70% for B30 and B100 respectively. While the PAH profiles for the neat diesel fuel and B30 were similar, the profile of B100 differed in the sense that the emission contained a higher percentage of PAHs with higher molecular weights. The emission of these PAHs was however larger using the neat diesel fuel with the exception for some of these higher molecular weight PAHs of which there was an increased emission using B100. Thermogravimetric analysis revealed that the collected particles from B100 contained a substantial amount of volatile components. A mass spectrometric full scan analysis suggests that these volatile components are in fact unburned or partially-burned fuel constituents. It is concluded that the particles originating from biodiesel combustion might be very different from those originating from petroleum diesel combustion which places new demands on the development of measurement methodologies originally developed for particulate emissions from petroleum-based fuels. (C) 2013 Elsevier Ltd. All rights reserved.