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The kinetics of Fe(III) precipitation in synthetic buffered waters have been investigated over the pH range 6.0-9.5 using a combination of visible spectrophotometry, Fe-55 radiometry combined with ion-pair solvent extraction of chelated iron and numerical modeling. The rate of precipitation, which is first order with respect to both dissolved and total inorganic ferric species, varies by nearly two orders of magnitude with a maximum rate constant of 16 +/- 1.5 x 10(6) M-1 s(-1) at a pH of around 8.0. Our results support the existence of the dissolved neutral species, Fe(OH)3, and suggest that it is the dominant precursor in Fe(III) polymerization and subsequent precipitation at circumneutral pH. The intrinsic rate constant of precipitation of Fe(OH)(3)(0) was calculated to be k(Fe(OH)30) = 2.0 x 10(7) M-1 s(-1) allowing us to predict rates of Fe(III) precipitation in the pH range 6.0-9.5. The value of this rate constant, and the variation in the precipitation rate constant over the pH range considered, are consistent with a mechanism in which the kinetics of iron precipitation are controlled by rates of water exchange in dissolved iron hydrolysis species. (c) 2005 Elsevier Inc. All rights reserved.