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A sampling system was developed to measure the evolution of the speciated hydrocarbon emissions from a single-cylinder SI engine in a simulated starting and warm-up procedure. A sequence of exhaust samples was drawn and stored for gas chromatograph analysis. The individual sampling aperture was set at 0.13 s which corresponds to ∼ 1 cycle at 900 rpm. The positions of the apertures (in time) were controlled by a computer and were spaced appropriately to capture the warm-up process. The time resolution was of the order of 1 to 2 cycles (at 900 rpm). Results for four different fuels are reported: n-pentane/iso-octane mixture at volume ratio of 20/80 to study the effect of a light fuel component in the mixture; n-decane/iso-octane mixture at 10/90 to study the effect of a heavy fuel component in the mixture; m-xylene and iso-octane at 25/75 to study the effect of an aromatics in the mixture; and a calibration gasoline.