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This study examines glycerol as an additive to diesel fuel to demonstrate it has the potential to suppress the formation of soot/PM. The investigation of a diesel/glycerol emulsion included an engine trial, high-speed imaging in an optical combustion chamber and a fundamental chemical kinetic study examining soot precursor formation. The emulsion had a longer ignition delay but higher AHRR with increasing load. There was no impact on the brake thermal efficiency. CO and THC were higher with the emulsion at the lower engine loads. The emulsion emitted a smaller number of particles with diameters greater than 25 nm, with a significant drop in the number of particles at 60 nm. The number of particles with diameters greater than 25 nm is reduced by 61% at 20 Nm, by 56% at 80 Nm, and by 11% at 140 Nm. A large peak of sub 10 nm particles, 2 orders of magnitude greater than with diesel alone, was observed, hypothesised to be semi-volatile organic compounds that have started to condense. A thermogravimetric analysis supported a larger semi-volatile content. Ignition delay time, determined from the OH* flame emission, was always longer for the emulsion at all conditions. In-flame soot was always lower with the emulsion at all conditions. Flame lift-off length decreased with increasing temperature and pressure of the ambient gas whilst soot increased. The concentration of known soot precursors, C2H2 and C2H4 was reduced but the concentrations of C3H6 and PC3H4 were not significantly affected. [ABSTRACT FROM AUTHOR]