Simultaneous measurement of the concentration of released atomic sodium, swelling, surface and internal temperature of a burning black liquor droplet under a fuel lean and rich condition has been demonstrated. Two-dimensional two-colour optical pyrometry was employed to determine the distribution of surface temperature and swelling of a burning black liquor droplet while planar laser-induced fluorescence (PLIF) was used to assess the temporal release of atomic sodium. The key findings of these studies are: (i) the concentration of atomic sodium released during the drying and devolatilisation stages was found to be correlated with the external surface area; and (ii) the insignificant presence of atomic sodium during the chat consumption stage shows that sodium release is suppressed by the lower temperature and by the high CO2 content in and around the particle. (c) 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.