Coprecipitation of Iron and Aluminum during Titration of Mixed Al3+, Fe3+, and Fe2+ Solutions

P. M. Bertsch1, W. P. Miller2, M. A. Anderson3 and L. W. Zelazny3
1 Division of Biogeochemistry, Savannah River Ecology Laboratory, University of Georgia, P.O. Drawer E, Aiken, South Carolina 29801
2 Department of Agronomy, University of Georgia, Athens, Georgia 30602
3 Department of Agronomy, Soil, and Environmental Sciences, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061

Abstract: Potentiometric titration analysis was used to examine the hydrolysis behavior of Fe2+ Fe3+, and Al3+ in pure solution and in mixture, in order to evaluate the potential for coprecipitation and mixed solid-phase formation. Mixtures of Fe3+ and Al3+ did not interact during neutralization; base consumed in their respective buffer regions was equivalent to the total metal added. Fe2+-Al3+ solutions, however, showed excess base consumption in the Al3+ buffer region, indicating hydrolysis of Fe2+ at lower than normal pH. Ferric/ferrous iron analyses of systems at the Al endpoint (pH 5.5) showed amounts of oxidized Fe equivalent to the excess base consumption (∼10% of total Fe), with substantial amounts of Fe2+ sorbed to or occluded within Al polymers present. Increased electrolyte levels or the presence of SO42- inhibited oxidation and sorption of Fe2+ on Al surfaces, suggesting that Fe hydrolysis and oxidation was catalyzed at the surfaces. Increasing Al3+: Fe2+ ratios in the titrated solutions also increased the amount of Fe2+ coprecipitation, supporting a surface-mediated reaction mechanism. Ferrous iron oxidation was sensitive to O2 levels, which also affected the amount of coprecipitation. These findings suggest that surface-facilitated oxidation of Fe2+ may be important in the formation of mixed Fe-Al mineral phases in dilute soil solutions.

Key Words: Aluminum • Hydrolysis • Iron • Oxidation • Potentiometric titration

Clays and Clay Minerals; February 1989 v. 37; no. 1; p. 12-18; DOI: 10.1346/CCMN.1989.0370102
© 1989, The Clay Minerals Society
Clay Minerals Society (www.clays.org)