The release of volatile sodium during coal combustion is a significant factor in the fouling and corrosion of heat transfer surfaces within industrial coal-fired boilers. A method for measuring the temporal release of atomic sodium from a single coal particle is described. Laser absorption was used to calibrate laser-induced fluorescence measurements of atomic sodium utilising the sodium D1 line (589.58 nm) in a purpose-designed flat flame environment. The calibration was then applied to planar laser-induced fluorescence measurements of sodium atoms in the plume from a single Victorian brown coal particle (53 mg) suspended within the flat flame. The peak concentration of atomic sodium was approximately 64.1 ppb after 1080.5 s, which appears to correspond to the end of char combustion. To our knowledge this is the first in situ quantitative measurement of the concentration field of atomic sodium in the plume above a burning particle. A simple kinetic model has been used to estimate the rate of sodium decay in the post-flame gases. Comparison of the estimated and measured decay rates showed reasonable agreement. (C) 2008 The Combustion Institute. Published by Elsevier Inc. All rights reserved.