Temporally resolved measurements of surface temperature, pellet diameter and proximal sodium concentration field are presented for the combustion of a high sodium coal (Zhundong) pellet. Non-resonant Planar laser-induced fluorescence (PLIF) was used to image the atomic sodium distribution around the coal pellet. The release profile of atomic sodium demonstrates three phases of combustion: (I) the de volatilization stage, (II) the char burnout stage, and (III) the ash reaction stage. Highest peak sodium concentration occurred in the char burnout stage, while the ash stage had the longest duration. The radial and axial sodium concentration decay during different phases of combustion was analyzed. During char burnout and ash stages, the maximum concentration of atomic sodium was near the pellet. In the devolatilization stage, burning of volatile-gases creates a high temperature region away from the surface of the coal pellet, which enhances the decomposition of sodium compounds in this region. Axial decay of atomic sodium concentration was governed by chemical reactions during all combustion stages. Calculation of atomic sodium flux (Na*(flux),) indicate that the smaller pellet releases atomic sodium more strongly in the devolatilization and char burnout stages than larger pellet. The mechanism of sodium release was inferred from the time derivatives of Na*(flux),,, pellet-surface temperature (T) and pellet diameter (d). During the devolatilization stage, only Na*(flux) and T show variations, indicating that atomic sodium release is due to pyrolysis of the coal pellet. In the char burnout stage, time derivatives of the three parameters obey a common trend, indicating that the sodium release is associated with the burning of organic components in the pellet. In the ash reaction stage, T and d remain constant, indicating that the release of atomic sodium may be attributed to slow processes in the ash, likely vaporization of sodium from crystalline solids. A two-steps sodium release kinetics has been developed in this study and the simulation results agree well with measurements at three burning stages of coal pellet. (C) 2016 The Combustion Institute. Published by Elsevier Inc. All rights reserved.