The quantitative measurement of atomic sodium (Na) release, at high concentration, from a burning black liquor droplet has been demonstrated using a planar laser-induced fluorescence (PLIF) technique, corrected for fluorescence trapping. The local temperature of the particle was measured to be approximately 1700 °C, at a height of 10 mm above a flat flame burner. The PLIF technique was used to assess the temporal release of atomic Na from the combustion of black liquor and compare it with the Na concentration in the remaining smelt. A first-order model was made to provide insight using a simple Plug Flow Reactor model based on the independently measured concentration of residual Na in the smelt as a function of time. This model also required the dilution ratio of the combustion products in the flat flame entrained into the plume gas from the black liquor particle to be estimated. The key findings of these studies are: (i) the peak concentration of atomic Na from the combustion of the black liquor droplets is around 1.4 ppm; (ii) very little atomic Na is present during the drying, devolatilisation or char combustion stages; and (iii) the presence of atomic Na during smelt phase dominates over that from the other combustion stages.