The temporal history of the release of volatile alkali species during coal combustion is a significant, but poorly understood factor in the fouling and corrosion of heat transfer surfaces within industrial coal-fired boilers. We present new results of the simultaneous measurement of particle temperature, particle size and the atomic sodium concentration in the plume of a burning coal particle. During the char phase, the sodium concentration in the plume was found to be linearly dependent on the inverse of particle diameter, but during the ash phase the sodium concentration was found to decay exponentially with decreasing particle temperature. The centreline decay of Na within the plume above the burning particle consists of one region controlled by a first order chemical reaction and a second region controlled by diffusion ; P.J. van Eyk, P.J. Ashman, Z.T. Alwahabi and G.J. Nathan ; Copyright © 2009 Elsevier B.V. All rights reserved