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In a Diesel engine with a Diesel particulate filter (DPF) system, high-sulfur fuel causes white smoke containing odorous and harmful pollutants during DPF regeneration. This study investigates the conditions and mechanisms of sulfur-related white smoke generation. Engine and vehicle tests found that sulfur compounds emitted from the engine accumulated on the catalysts in the DPF system and were emitted as white smoke during DPF regeneration. The white smoke was observed when the catalyst temperature was more than 450°C, under conditions such as the early stage of DPF regeneration. Model gas tests were conducted to clarify the mechanism of the white smoke. It was found that SO2 emitted from the engine was oxidized to SO3 on the catalyst, which was then mainly absorbed on the oxidation catalyst support (Al2O3). Then, the absorbed SO3 was desorbed and converted into white smoke.