In the present paper, confined dry Cu nanoaerosols of controlled particle size are inspected under a time-resolved LIBS scheme to explore the effect of laser-particulate matter interaction upon the detection capability of airborne nanoparticulate material. Optically catapulted streams probed showed linear intensity vs mass correlation and similar signal stability which is linked to the seeding effect caused by smaller particles yielding hotter, albeit shorter plasmas. Seeding effect is demonstrated by hyperspectral time-resolved aerosol inspection, which exposes both, the interaction between multiple plasma nuclei and the discrete nature of the laser-particle interaction. Observed population/exhaustion cycles at the focal volume of the inspection laser explained the uncertainty values characteristic of LIBS inspection of aerosols. A thorough inspection of the emission in time evidenced a significantly different evolution of the intensity profile for commonly monitored Cu lines owed not only to the nature of the monitored transit and pulse energy, but also to particle size. These results suggest that the experimental settings for quantitative ultrafine aerosol inspection need to be tuned according to the target particle size and the particle density of the aerosol as seeding effects facilitates signal saturation, therefore this effect simultaneously contributes to and detracts from the analytical performance of LIBS on nanometric aerosols.
