Elemental fractionation in aerosol laser-induced breakdown spectroscopy with nanosecond and femtosecond laser ablation

[Display omitted] •Elemental fractionation in aerosol LIBS is reduced by more than 50% using fs-LA.•Changes to local plasma temperatures and electron densities are determined for binary particle matrices.•Elemental fractionation is shown to be dependent on atomic energy levels.•Preliminary results of molecular emission fractionation from TiO and AlO are presented. For the purpose of realizing atmospheric radiation plume tracking, laser-induced breakdown spectroscopy (LIBS) was performed to characterize Cs atomic emissions from airborne nanoparticles in a binary particle matrix using nanosecond and femtosecond laser ablation. As a surrogate to multi-element nuclear fallout particulates, both Cs and Na solutions were mixed with Cu at a 1:1.45 M concentration ratio and aerosolized to study elemental fractionation in atomic emissions, revealing Na I resonance emissions are enhanced whereas Cs I resonance emissions are reduced with Cu present despite sharing similar electronic and chemical properties. Femtosecond laser ablation reduced elemental fractionation effects by more than 50% while retaining the same temporal fractionation trends for Cs and Na. The origin of elemental fractionation in aerosol LIBS was further investigated using Al and Ti aerosols which revealed that the particle matrix induces changes to the local plasma temperature, population of atomic states, and subsequent molecular association and emission.