Mechanistic understanding of sunlight-induced natural processes for production of dissolved gaseous mercury (DGM) in freshwaters has remained limited, and few direct field tests of the mechanistic hypotheses are available. We exposed ferric iron salt-spiked fresh surface lake water (Whitefish Bay, Lake Superior, MI) in Teflon bottles and pond water (Oak Ridge, TN) in quartz bottles to sunlight in the field to infer if sunlight and Fe(III)-induced photochemical production of DGM could mechanistically contribute partly to natural photochemical production of DGM in freshwaters. We found that exposure of freshwater spiked with fresh Fe(III) (approximately 5 or 10 microM) to sunlight led to repeatable, significantly larger increases in DGM production (e.g., 380% in 1 h, 420% in 2 h, and 470% in 4 h for Whitefish Bay water) than exposure without the spike (e.g., 200% in 6 h). DGM increased with increasing exposure time and then often appeared to approach a steady state in the tests. Higher Fe(III) spike levels resulted in the same, or even less, DGM production. Storage of the water with or without Fe(III) spike in the dark after sunlight exposure led to significant, apparently first-order, decreases in DGM. These phenomena were hypothetically attributed to sunlight-induced photochemical production of highly reducing organic free radicals through photolysis of Fe(III)-organic acid coordination compounds and subsequent reduction of Hg(II) to Hg(0) by the organic free radicals; the reduction was also accompanied by dark oxidation of Hg(0) by photochemically originated oxidants (e.g., .OH). This study suggests that sunlight and Fe(III)-induced photochemical reduction of Hg(II) could be one of the mechanisms responsible for natural photochemical production of DGM in freshwaters and that Fe species may be influential in mediating Hg chemodynamics and its subsequent toxicity in aquatic ecosystems.