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Influence of Organic 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 organic anions were investigated with the intent of distinguishing mononuclear and polynuclear Al. Mononuclear Al solutions containing malate, glutarate, succinate, salicylate, formate, malonate, and fulvate with ligand/Al molar ratios ranging from 0.4 to 7.5, reacted rapidly with ferron and were modeled using a single second-order equation. Similarily, mononuclear Al solutions containing citrate, tartarate, and oxalate with ligand/Al molar ratios 0.13, 0.08, and 0.38, respectively, also reacted rapidly with ferron and were modeled using a single second-order expression. Model fitted k_a values (rate of Al-monomer reactions with ferron) for these organic-Al solutions were similar to k_a values determined for uncomplexed mononuclear Al solutions without added organic ligands. Increasing concentrations of citrate, tartarate, and oxalate that cause the ligand/Al molar ratios to exceed the critical values of 0.13, 0.08, and 0.38, respectively, form complexes with Al that are not easily degraded by ferron, thus limiting the credibility of accurate distinction between monomeric and polymeric Al. The interaction of ferron with Al-polymers was not significantly affected by concentrations of organic anions whose ligand/Al molar ratio did not exceed these critical values. These conditions allowed the accurate distinction of mononuclear and polynuclear Al.

¹ Contribution from the Dep. of Agronomy, Virginia Polytechnic Inst. and State Univ., Blacksburg, VA 24061. This research was funded in part by U.S. Dep. of Energy and contract no. DE-AS05-83ER60170.

² Postdoctoral Research Associate and Professor of Agronomy. 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.

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