Redox Chemistry of Iron in Fog and Stratus Clouds

The redox chemistry of Fe in fog and cloudwater has been investigated at coastal and inland locations in the Los Angeles basin, in Bakersfield California, and in Delaware Bay. Samples were collected and analyzed for Fe (Fe(II), Fe(III), total Fe), sulfur (S(IV), S(VI)), organic ligands (formate, acetate, oxalate), total organic carbon (TOC), pH, major cations (sodium, calcium, magnesium, potassium, ammonium), chloride, sulfate, nitrate, peroxides, and aldehydes (HCHO); the amount of sunlight was also measured. The ratio Fe(II)/Fe(total) varied between 0.02 and 0.55. The concentration of Fe(II) varied between 0.1 and 5 micromole, and the concentration of total Fe varied between 2 and 27 micromole. The atmospheric redox cycle of Fe involves both dissolved and aerosol surface species and appears to be related to the presence of organic compounds which act as electron donors for the reduction of Fe(III). Fe(III) reduction is enhanced by light but significant Fe(II) levels were observed in the dark. We suggest hat reduction of Fe(II!) species by organic elecU'on donors may be an important pathway that affects the speciation of Fe in both urban and rural atanospheres. It is possible that reactions involving Fe and organic compounds might be an important source of carboxylic acids in the troposphere.