A statistical analysis of ambient air particle monitoring, namely PM2.5, is presented to elucidate the correlations between laser-induced breakdown spectroscopy (LIBS)-based speciated aerosol monitoring and non-speciated aerosol monitoring (i.e., total particle counts). LIBS was used in a real-time, conditional-processing mode to identify individual aerosol particles containing detectable quantities of either calcium or sodium, as based on the resulting atomic emission signals. Using this technique, real-time measurements of speciated aerosol particle concentrations and analyte mass concentrations were evaluated for a total of 60 1-hour sampling periods spread over a 5-week period. For each 1-hour sampling period, total aerosol counts were simultaneously monitored using a commercial light scattering-based instrument. Over the 30 sampling periods, aerosol counts (both total and LIBS-based) were found to vary by more than one order of magnitude. For aerosol particles in the 500 nm to 2.5 microm size range, significant correlations were found between the two sampling methods, resulting in correlation coefficients (r2) ranging from 0.22 to 0.93. In addition, transient fluctuations in aerosol counts on a timescale of 5 to 10 minutes were successfully observed simultaneously with the two monitoring techniques, thereby demonstrating the temporal resolution of LIBS.