A multi-photon ionization based fast conductance (MPIFC) technique was applied to detect combustion byproduct aerosols. These PAH-polluted aerosols were on-line sampled by means of renewable water microdroplets. The environmental cases considered here have involved such common air contaminants as motor car exhaust gas and cigarette smoke. The possibility of obtaining useful calibration curves has been addressed. Two droplet contamination regimes were clearly observed. These have been argued to be associated with either a volume uniform (i.e., a bulk type) or a surface-favored contamination. The latter regime is possible whenever the increasing droplet contamination extends beyond the solubility saturation of the PAH compounds. Detection limits as low as 1 pg were obtained for pyrene-contaminated renewable microdroplets.