Alkali vapors present in the flue gas generated during coal-based combustion form fouling deposits as they condense. An additive added to coal can trap alkali elements in ash, therefore suppress the growth rate of fouling deposits, and increase thermal efficiency of a coal-fired thermal power plant. Laser-induced breakdown spectroscopy (LIBS) technique is proposed and demonstrated to screen potential additives to trap alkali elements in ash. Five additives—namely, kaolinite, alumina, silica, magnesia, and pumice—were analyzed for their effectiveness on four Indian coals for retaining/confining alkali elements in ash during coal combustion. Ratio analysis based on LIBS emission intensity values clearly shows that kaolinite and pumice are promising additives to trap sodium. Similarly, kaolinite, pumice, and silica exhibited good potassium retention. © 2016, Springer-Verlag Berlin Heidelberg.