Photochemical activation of chlorine by iron-oxide aerosol

Abstract

The photochemical activation of chlorine by dissolved iron in artificial sea-salt aerosol droplets and by highly dispersed iron oxide (Fe2O3) aerosol particles (mainly hematite, specific surface ~150 m2 g−1) exposed to gaseous HCl, was investigated in humidified air in a Teflon simulation chamber. Employing the radical-clock technique, we quantified the production of gaseous atomic chlorine (Cl) from the irradiated aerosol. When the salt aerosol contained Fe2O3 at pH 6, no significant Cl production was observed, even if the dissolution of iron was forced by “weathering” (repeatedly freezing and thawing for five times). Adjusting the pH in the stock suspension to 2.6, 2.2, and 1.9 and equilibrating for one week resulted in a quantifiable amount of dissolved iron (0.03, 0.2, and 0.6 mmol L−1, respectively) and in gaseous Cl production rates of ~1.6, 6, and 8 × 1021 atoms cm−2 h−1, respectively. In a further series of experiments, the pure Fe2O3 aerosol was exposed to various levels of gaseous hydrogen chloride (HCl). The resulting Cl production rates ranged from 8 × 1020 Cl atoms cm−2 h−1 (at ~4 ppb HCl) to 5 × 1022 Cl atoms cm−2 h−1 (at ~350 ppb HCl) and confirmed the uptake and conversion of HCl to atomic Cl (at HCl to Cl conversion yields of 2–5 %, depending on the relative humidity). The Fe2O3 experiments indicate that iron-induced Cl formation may be important for highly soluble combustion-aerosol particles in marine environments in the presence of gaseous HCl.