Accurate knowledge of the concentrations of potassium and other elements is critical for evaluating the effects of straw and other high-fouling biomass fuels in combustion boilers and other thermal systems. Development of accurate and precise analytical procedures is therefore essential for utilization of biomass fuels in energy production and high-temperature applications. By comparing the results of X-ray fluorescence (XRF) analyses with similar analyses done using instrumental neutron activation (INA), it is observed that 20-25% of the original K2O content of straw ashes and slag can be lost during sample preparation for analyses. The loss occurs during heating of the ashes to determine loss on ignition probably as a result of the breakdown of sylvite (KCl). This loss can be significantly reduced, but not completely eliminated, if the analyses are performed on ashes that have not previously been heat-treated. The study poses the cautionary note that similar losses may occur during XRF analyses of other agricultural and soil samples containing high amounts of alkali halogens.