Kinetics of photochemical/chemical cycling of iron coupled with organic substances in cloud and fog droplets

Computer Science

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Scientific paper

The kinetics of photochemical reduction of Fe(III) coupled with organic ligands has been investigated to understand the photoredox cycling of Fe and the significance of this cycling in the production of photo-oxidants and transformation of S(IV) and organic pollutants in atmospheric waters. The photoreduction of ferrioxalate ion is first order with respect to Fe(III) and has a rate constant of 4.0 ± 0.4 × 10 -2 s -1 in anoxic solutions at summer clear-day-noon time. In the presence of oxygen, the oxalate radical formed in the primary photoreaction further reduces O 2 to HO . 2 /O . - 2 , leading to the reoxidation of Fe(II) and the formation of H 2 O 2 . At a photochemical steady-state, the ratio of Fe(II)/Fe(III) is determined by: where subscript ss denotes steady-state, k s and k 9 are the rate constants for photoreduction of Fe(III) complex and the oxidation of Fe(II) by HO . 2 /O . - 2 , respectively, and [HO . 2 /O . - 2 ] is the concentration of HO . 2 /O . - 2 . During sunny daytime, a large fraction of Fe is present as Fe(II), which provides a significant source of dissolved Fe(II) for the primary productivity in surface water systems.

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