Iron(III)-induced activation of chloride and bromide from modeled salt pans.

The photochemistry of halides in sea spray aerosol, on salt pans, and on other salty surfaces leads to a formation of reactive halogen species. We investigated the photochemical formation of atomic chlorine (Cl) and bromine (Br) in the gas phase in the presence of laboratory-modeled salt pans consisting of sodium chloride doped with iron(III) chloride hexahydrate (0.5 and 2 wt %). The samples were spread on a Teflon sheet and exposed to simulated sunlight in a Teflon smog chamber in purified, humidified air in the presence of a test mixture of hydrocarbons at the ppb level to determine Cl, Br, and OH formation by the radical clock method. Driven by the photolytic reduction of Fe(III) to Fe(II), the production rates of the Fe(III)-doped NaCl salt samples (up to10(7) atoms cm(-3) s(-1)) exceeded the release of Cl above a pure NaCl sample by more than an order of magnitude in an initially O3-free environment at low NOX. In bromide-doped samples (0.5 wt % NaBr), a part of the Cl release was replaced by Br when Fe(III) was present. Additions of sodium sulfate, sodium oxalate, oxalic acid, and catechol to NaCl/FeCl3 samples were found to restrain the activation of chloride.