A quantitative point measurement of total sodium ([Na]_total) and potassium ([K]_total) in the plume of a burning particle of Australian Loy Yang brown coal (23 ± 3 mg) and of pine wood pellets (63 ± 3 mg) was performed using laser-induced breakdown spectroscopy (LIBS) in a laminar premixed methane flame at equivalence ratios (Φ) of 1.149 and 1.336. Calibration was performed using atomic sodium or potassium generated by evaporation of droplets of sodium sulfite (Na₂SO₃) or potassium sulfate (K₂SO₄) solutions seeded into the flame. The calibration compensated for the absorption by atomic alkalis in the seeded flame, which is significant at high concentrations of solution. This allowed quantitative measurements of sodium (Na) and potassium (K) released into the flame during the three phases of combustion, namely devolatilization, char, and ash cooking. The [Na]_total in the plume released from the combustion of pine wood pellets during the devolatilization was found to reach up to 13 ppm. The maximum concentration of total sodium ([Na]^max_total) and potassium ([K]^max_total) released during the char phase of burning coal particles for Φ = 1.149 was found to be 9.27 and 5.90 ppm, respectively. The [Na]^max_total and [K]^max_total released during the char phase of burning wood particles for Φ = 1.149 was found to be 15.1 and 45.3 ppm, respectively. For the case of Φ = 1.336, the [Na]^max_total and [K]^max_total were found to be 13.9 and 6.67 ppm during the char phase from burning coal particles, respectively, and 21.1 and 39.7 ppm, respectively, from burning wood particles. The concentration of alkali species was higher during the ash phase. The limit of detection (LOD) of sodium and potassium with LIBS in the present arrangement was estimated to be 29 and 72 ppb, respectively.