Iron(III)-induced activation of chloride from artificial sea-salt aerosol

Abstract

Environmental context Inorganic, natural aerosols (sea-salt, mineral dust, glacial flour) and contributions of anthropogenic components (fly ash, dust from steel production and processing, etc.) contain iron that can be dissolved as FeIII in saline media. This study investigates photochemical processes in clouds and aerosols producing gas-phase Cl as a function of salt- and gas-phase composition employing a simulation chamber. Atomic Cl may contribute to the oxidative capacity of the troposphere, and our findings imply local sources. Abstract Artificial sea-salt aerosol, containing FeIII at various compositions, was investigated in a simulation chamber (made of Teflon) for the influence of pH and of the tropospheric trace gases NO2, O3 and SO2 on the photochemical activation of chloride. Atomic chlorine (Cl) was detected in the gas phase and quantified by the radical clock technique. Dilute brines with known FeIII content were nebulised until the relative humidity reached 70–90%. The resulting droplets (most abundant particle diameter: 0.35–0.46µm, initial surface area: up to 3×10–2cm2cm–3) were irradiated with simulated sunlight, and the consumption of a test mixture of hydrocarbons was evaluated for Cl, Br and OH. The initial rate of atomic Cl production per aerosol surface increased with FeIII and was ~1.9×1018 atoms cm–2s–1atCl–/FeIII=13. The presence of NO2 (~20 ppb) increased it to ~7×1018 atoms cm–2s–1, the presence of O3 (630 ppb) to ~9×1018 atoms cm–2s–1 and the presence of SO2 at 20 and 200 ppb inhibited the release slightly to ~1.7 and ~1.1×1018 atoms cm–2s–1. The observed production of atomic Cl is discussed with respect to pH and speciation of the photolabile aqueous FeIII complexes.