Response of the unattached 218Po activity size distribution in H2O-SO2-N2 atmospheres

The response of the unattached 218Po activity size distribution to variations in H2O and SO2 concentration was investigated in a high-purity N2 atmosphere. Lognormal size distributions were reconstructed from screen diffusion battery data using a random search and optimization procedure. For relative humidities of 1% to 90%, SO2 concentrations of 0-6 ppm, and residence times of 38 s, median diameters of the unattached mode ranged from 0.50 (+/- 0.04) to 0.80 (+/- 0.06) nm, corresponding to diffusion coefficients of 0.1-0.05 cm2 s-1. Increases in water vapor concentration resulted in an enhanced rate of ion neutralization and suppression of ion cluster formation. Decreases in cluster diameter with increasing humidity were therefore observed. Addition of SO2 at constant relative humidity resulted in an initial increase in diameter, with a subsequent decrease. Geometric standard deviations averaged 1.05 (+/- 0.01) to 1.06 (+/- 0.01) in all cases, with the unattached fraction comprising 83% to 88% of the total distribution. Results suggest that increases in water vapor concentration enhance neutralization in the immediate vicinity of the recoil path through water radiolysis. Conversion of OH to H2OSO4 on addition of SO2 provides a binary condensable phase capable of clustering around the ion at low relative humidities, increasing particle size. High H2O and SO2 concentrations enhance neutralization through electron scavenging and subsequent ion collision near the end of the recoil path, decreasing the number of available cluster sites and suppressing cluster formation. This reduction is more significant than the increasing size of the stable ion cluster, with increasing H2O and H2SO4 concentrations as predicted by Raes, resulting in decreases in both median diameter and distribution spread.