A kinetic method of analysis which distinguishes Fe(II) from Fe(III) and Fe(III) forms of various labilities from each other is based on spectrophotometric monitoring of the reaction of Fe(II) with ferrozine. Reduction of Fe(III) with hydroxylamine hydrochloride allows the single colourimetric reagent to detect all forms of Fe. The method is applied to study of the effects of a well characterized soluble soil organic acid sample, a fulvic acid, on the speciation of Fe(III) under conditions (pH = 6) where Fe(III) forms a colloidal hydrous oxide in the absence of fulvic acid. The effect of fulvic acid is to greatly increase the lability of Fe(III) compared to that in a hydrous oxide colloid. However, ultrafiltration and light scattering experiments indicate that the Fe(III) – fulvic acid species is larger than the hydrous ferric oxide colloid particles. Kinetic studies in the absence of hydroxylamine hydrochloride show that fulvic acid can act as a reducing agent for iron in the presence of an Fe(II) complexing agent like ferrozine but neither kinetic studies with an Fe(III) reagent nor Mössbauer spectra suggest significant initial presence of Fe(II) in the aged Fe(III) – fulvic acid samples.
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