Pure sunflower oil was used in a Perkins 4-236 DI diesel engine at 2200 rpm and maximum power, particulate samples at 50°C were obtained from the exhaust 7m from the exhaust port in an air cooled exhaust pipe. The engine lubricating oil was fresh and contained no fuel contamination. The sunflower oil had higher particulate, UHC, CO and NOx emissions than for diesel. This was attributed to the shorter ignition delay and higher diffusive burning. The higher UHC emissions also resulted in a higher particulate SOF. Sunflower oil contained no fuel PAH above 1 ppm and there was no source of PAH from the lubricating oil. However, significant PAH emissions were found in the particulate SOF, but at a level well below that for diesel. It was shown that the bulk of this PAH could be attributed to the thermal desorption of PAH from the exhaust pipe walls. Hence, there was little PAH generated by pyrosynthesis as part of the combustion process.