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Kinetics of the Abiotic Reduction of Polymeric Manganese Dioxide by Nitrite: An Anaerobic Nitrification Reaction

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Abstract

Manganese oxides are strong environmental oxidants recently found to be involvedin the nitrogen cycle. Of the several possible reactions with reduced nitrogen species,the reduction of MnO2 by nitrite has only received marginal attention. Yet, this reaction might explain why nitrification can occur in the absence of O2, observed in both sediments and water columns. We have determined the stoichiometry of this reaction, as well as the chemical kinetics and the activation parameters, using a soluble polymeric form of MnO2. The reaction rate decreases with increasing pH and decreasing temperature. The reaction is first order in each reactant with a second order rate constant (k) = 493 M-1 min-1 at 21.5 °C and pH = 5.00. The energy of activation (Ea = 9.370 kJ/mole) and the entropy of activation (Δ S‡ = -169.5 J/mole) show the reaction to be associative and diffusion controlled, occurring via an inner-sphere mechanism, likely with O atom transfer from MnO2 to HNO2. The reaction is proton assisted and slowsdown at pH ≥ 5.5 where NO2 - and MnO2 (unprotonated and negatively charged) become the dominant species. In natural waters and sediments where anaerobic nitrification has been observed the pH is higher than this. Thus, the thermodynamically favorable reaction will likely proceed by microbial mediation.

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  1. College of Marine Studies, University of Delaware, 700 Pilottown Rd., Lewes, DE, 19958, U.S.A

    George W. Luther III & Jeannette I. Popp

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  1. George W. Luther III
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  2. Jeannette I. Popp
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Luther, G.W., Popp, J.I. Kinetics of the Abiotic Reduction of Polymeric Manganese Dioxide by Nitrite: An Anaerobic Nitrification Reaction. Aquatic Geochemistry 8, 15–36 (2002). https://doi.org/10.1023/A:1020325604920

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