Nanosecond laser-induced breakdown spectroscopy has been examined for the analysis of suspended matter in a free stream of air. The real-time monitoring of this scenario poses major challenges for an accurate categorization due to its changing characteristics such as composition, size, and density of particles. The effects of particle size and matrix in the optical emission responses registered from such scenarios have been evaluated. Distant (10 m) plasmas of saline solutions, containing either NaCl or Na2SO4 at different concentrations, have been induced by nanosecond laser pulses at a wavelength of 1064 nm. The effects of the droplet size and its concentration on differences in the laser-induced breakdown probability, the intensity of the characteristic lines, and the plasma emission continuum have been discussed. The quantification of sodium in distant water droplets has been proved. However, an initial knowledge on the average droplet size is required. The average droplet size could be determined from the slope of H I and O I lines versus the continuum plasma emission, which is only weakly influenced by the salt content in the droplets.