Tunable diode laser absorption spectroscopy (TDLAS) was used for quantitative in-situ detection of gaseous elemental potassium (K) at distances 2-11 mm above biomass pellets combusted in a macro-thermogravimetric analyzer (macro-TGA). Single pellets of energy wood (EW) and wheat straw (WS) were converted in air at a furnace temperature of 850 °C and a carrier flow rate of 15 liters per minute. A second TDLAS system measured water vapor concentration and temperature above the pellets. In addition, semi-time-resolved K release data was obtained from conventional ICP-MS/AES analysis of fuel/ash residues collected at several occasions during devolatilization and char combustion. It was found that the fuels differ with respect to relative K-release and temporal release histories. Significant concentrations of K(g) were detected with TDLAS above the pellets during devolatilization, but no K(g) was observed during char combustion, independent of the fuel type. The amount of K(g)tot measured above the pellets during devolatilization was larger for EW than for WS, even though the total K content of WS was a factor of 60 higher. By combining TDLAS and ICP data, and supported by equilibrium calculations, these results indicate that, during devocalization, K is mainly released as KCl from wheat straw, whereas both KCl and KOH are released from energy wood.