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Pulverized bituminous coal was burned in a 10 W externally heated entrained flow furnace under air-combustion and three oxy-combustion inlet oxygen conditions (28, 32, and 36%). Experiments were designed to produce flames with practically relevant stoichiometric ratios (SR = 1.2-1.4) and constant residence times (2.3 s). Size-classified fly ash samples were collected, and measurements focused on the soot, elemental carbon (EC), and organic carbon (OC) composition of the total and ultrafine (< 0.6 mu m) fly ash. Results indicate that although the total fly ash carbon, as measured by loss on ignition, was always acceptably low (< 2%) with all three oxy-combustion conditions lower than air-combustion, the ultrafine fly ash for both air-fired and oxy-fired combustion conditions consists primarily of carbonaceous material (50-95%). Carbonaceous com-ponents on particles < 0.6 mu m measured by a thermal optical method showed that large fractions (52-93%) consisted of OC rather than EC, as expected. This observation was supported by thermogravimetric analysis indicating that for the air, 28% oxy, and 32% oxy conditions, 14-71% of this material may be OC volatilizing between 100 degrees C and 550 degrees C with the remaining 29-86% being EC/soot. However, for the 36% oxy condition, OC may comprise over 90% of the ultrafine carbon with a much smaller EC/soot contribution. These data were interpreted by considering the effects of oxy-combustion on flame attachment, ignition delay, and soot oxidation of a bituminous coal, and the effects of these processes on OC and EC emissions. Flame aerodynamics and inlet oxidant composition may influence emissions of organic hazardous air pollutants (HAPs) from a bituminous coal. During oxy-coal combustion, judicious control of inlet oxygen concentration and placement may be used to minimize organic HAP and soot emissions. (C) 2016 by The Combustion Institute. Published by Elsevier Inc.