Ferrate(VI) oxidation of glycine and glycylglycine: kinetics and products.

Amino acids and peptides may form potentially harmful disinfection byproducts during the conventional treatment of water and wastewater. Removal of these parent compounds by the use of the environmental-friendly oxidant, ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was assessed by studying the kinetics of the oxidation of glycine (NH(3)(+)CH(2)COOH, Gly) and glycylglycine (NH(3)(+)CH(2)CONHCH(2)COOH, Gly-Gly) as a function of pH (4.0-12.4) at 25 degrees C. This study with Gly-Gly represents an initial investigation of oxidation of peptides by Fe(VI). Generally, the second-order rate constant (k) increased with decreased pH in the basic pH region, but this trend was reversed in the acidic pH range. Consideration of the reactivity of three oxidants (H(2)FeO(4), HFeO(4)(-), and FeO(4)(2-)) with three species of Gly and Gly-Gly (positive, neutral, and negative) reasonably explained the pH dependence of the rates. At pH 9.0, the molar consumption of Fe(VI) was nearly equal to that of Gly. The reaction of Fe(VI) with Gly at molar ratios of 1.0 and 2.0 ([Fe(VI)]:[Gly]) produced ammonia, carbon dioxide, and acetate. A reaction scheme is proposed which explains the formation of these products. The values of k for oxidation of iminodiacetate and nitriloacetate at pH 7.0 were also determined in order to compare oxidation of amines by Fe(VI). The calculated half-lives at neutral pH for the oxidation of primary and secondary amines were in seconds while decomposition of tertiary amines would occur in minutes. Overall, the reactivity of Fe(VI) with Gly and Gly-Gly indicates the significant potential of Fe(VI) to remove amine- and peptide-containing pollutants in water and wastewater. (c) 2009 Elsevier Ltd. All rights reserved.