In oxycombustion and gasification processes coal pyrolysis occurs in CO2-rich atmospheres. The present work investigates the effect of such conditions on the quantity and quality of the submicronic carbon particulate produced. Pyrolysis experiments were carried out in either N-2 or CO2 atmospheres in a laminar drop tube reactor, with wall temperatures of 1573 K, heating rates of 10(4)-10(5) K/s and residence times below 130 ms, so as to reproduce pyrolysis conditions comparable to those of pulverized coal-fired boilers. The carbon particulate sampled in the reactor was found to have bimodal distribution in the micronic and submicronic ranges. A method based on solvent extraction was applied to carbon particulate for separating the two modes and determining the relative mass contribution of micronic and submicronic fractions. In CO2 atmosphere the amount of submicronic fraction of carbon particulate, referred to as soot, was found to be up to four times as much as upon N-2 experiments. Beside the larger formation of soot, relevant differences in terms of combustion reactivity, size distribution and chemical structure of the residual carbon particulate produced in CO2 environment in respect to N-2 environment were observed by means of a large array of techniques including thermogravimetry, microscopy (SEM+EDX), FT-IR, UV-visible and Raman spectroscopy along with XRD and XPS techniques. (C) 2016 The Combustion Institute. Published by Elsevier Inc. All rights reserved.