The Effect of Nucleating Particulates on Photochemical Aerosol Formation

The role of nucleating particulates in the formation of photochemical aerosols has been studied in a steady, laminar flow of ultrafiltered air containing NO₂ and octene-1 in the concentration range of (30 to 170 ppm) when subjected to intense irradiation under isothermal conditions. The particulates consisted of monodisperse polystyrene latex (d = 0.36 μ.) in concentrations similar to those in the atmosphere (6 × 10¹ to 3 × 10³ cm^–3); the irradiation intensity varied between (6 to 40 × 10³ lumen/liter) and the mean exposure duration between 30 and 180 sec. Samples of the flow prior to and after its photoactivation were withdrawn either by an Aerosol Spectrometer (AS) or by a Royco Aerosol Photometer (PH). While these indications refer thus to the same system, they differ, because the photometric data include all colloidal components in the airborne state, whereas the counts obtained from the AS deposits refer only to the nucleated latex particles. The following pattern becomes evident: The photochemical reaction yields fractional products (less than three percent) which have the tendency to agglomerate (or polymerize) due to their relatively low volatility—independent of the presence or absence of nucleating particulates. In their presence, this reaction becomes kinetically more probable and thus faster, hence the accumulant formation occurs preferably on the nuclei and causes their growth such that, e.g., a 10-fold higher nuclei concentration will produce under the same conditions 10 times the accumulant mass while autonucleation is suppressed. The growth process appears thus principally different from that of fog formation by H₂O-condensation, whereas for identical super saturation it is inversely proportional to the nuclear concentration. In the absence of nuclei autonucleation, i.e., self-agglomeration, occurs at a much lesser reaction rate and higher photon demand. The growth rate of the nuclei, when present, depends on the concentration of the oxidation catalyst (NO₂), its interaction with the nuclei surface is indicated. Under identical conditions the mass of nuclear accumulant is directly proportional to the concentration of the reactive hydrocarbon, while the growth rate depends on the light intensity and the exposure duration. The findings indicate that density and nature of particulate matter present in an air mass prior or during photo-activation are—aside from the chemical reactant levels—of major significance in aerosol formation.