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Influence of Inorganic Anions on the Speciation of Mononuclear and Polynuclear Aluminum by Ferron¹

ABSTRACT

The kinetic reactions of ferron (8-hydroxy-7-iodo-5-quinoline-sulfonic acid) with unneutralized and partially neutralized Al solutions in the presence of various inorganic anions were investigated for the purpose of differentiating mononuclear and polynuclear Al. Development of a general order reaction function indicated that ferron interactions with Al were modeled best by second-order rate expressions. Mononuclear Al solutions containing ClO^-₄, Cl^-, NO^-₃, SO^2-₄, H₂PO^-₄, and F^- with anion to Al molar ratios of 13, 21, 15, 5, 0.75, and 0.08, respectively, expressed similar reactions with ferron that conformed to a single second-order reaction. Ferron interactions with partially neutralized Al-anion solutions were described by two simultaneous second-order reactions that provided the rate of Al-polymer interactions with ferron, k_b, and the mole fraction of mononuclear Al species present, f_a. Distinction of mononuclear and polynuclear Al in partially neutralized solutions with various anions is possible using ferron if the H₂PO^-₄/Al and F^-/Al molar ratios do not exceed 0.75 and 0.08, respectively. Phosphate and F^- concentrations that reduce these ratios and SO^2-₄/Al ratios of 5 still form complexes with Al, but are easily degraded by ferron and react identically to uncomplexed mononuclear Al solutions. Such complexes must be accounted for if an estimate of toxic mononuclear Al [Al(H₂O)³⁺₆, AlOH(H₂O)²⁺₅, Al(OH)₂(H₂O)⁺₄] is desired.

¹ Contribution from the Dep. of Agronomy, Virginia Polytechnic Inst. and State Univ., Blacksburg, VA 24061. This research was funded in part by the U.S. Dep. of Energy under contract no. DE-ASOS-83ER60179.

² Postdoctoral Research Associate and Professor, respectively. Current address of the senior author is Oak Ridge National Lab., Environmental Sci. Div., P.O. Box X, Oak Ridge, TN 37831.

Received for publication September 17, 1986.