Significant concentrations of Fe(II) were produced upon irradiation of authentic rainwater with simulated sunlight. The magnitude of photoproduction was dependent on initial Fe(II), Fe(III), and hydrogen ion concentrations, with more Fe(II) photoproduction when initial Fe(III) and H+ concentrations were high and initial Fe(II) concentrations were low. An equation was developed that accurately predicts photoproduction of Fe(II) in rainwater based on initial Fe speciation values and pH. The quantum yield of Fe(II) photochemical production in rain decreased dramatically with increasing wavelength and decreasing energy of incoming radiation with the average quantum yield at 265 nm approximately an order of magnitude greater than at 546 nm. Probable photochemical precursors of Fe(II) in authentic rain include iron(III) oxalate, iron(III) hydroxide, and an undefined Fe(III) complex. The wavelength-dependent Fe(II) production was modeled using the average Fe(II) efficiency spectrum, an average rainwater absorption spectrum, and the modeled actinic flux for temperate latitudes in both summer and winter. The response spectrum has the highest photoproduction of Fe(II) in summer and winter at 325 and 330 nm, respectively, with greater production in summer rain due to increased actinic flux and longer hours of irradiation.
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