To simulate and better understand toxic metal-sorbent particle interactions, laser-induced breakdown spectroscopy (LIBS) was implemented to quantify trace amounts of manganese enriched on the surface of concomitant silica microsphere particles in an optical access laboratory-scale combustion system. Flame atomic absorption measurements verified that introduced manganese nanoparticles were extensively dissociated within the high-temperature region of the H-2-O-2-N-2-air fiame. LIBS-based conditional spectral analysis was performed using the Si (1) 288.1 nm atomic emission line with a spectral window containing both silicon and manganese atomic emission lines. The presence of silicon was found to have no effect on the emission intensity of the Mn triplet near 279 nm. The enrichment of manganese on the silica particles