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Time resolved changes in unburned hydrocarbon emissions and their components were investigated in a DI diesel engine with a specially developed gas sampling system and gas chromatography. The tested transient operations include starting and increasing loads. At start-up with high equivalence ratios the total hydrocarbon (THC) at first increased, and after a maximum gradually decreased to reach a steady state value. Reducing the equivalence ratio of the high fueling at start-up and shortening the high fueling duration are effective to reduce THC emissions as long as sufficient startability is maintained. Lower hydrocarbons, mainly C1-C8, were the dominant components of the THC and mainly determined the THC behavior in the transient operations while the proportion of hydrocarbon (HC) components did not significantly change. The unregulated toxic substances, 1,3 butadiene and benzene were detected in small quantities.