Electron accepting capacity of dissolved organic matter as determined by reaction with metallic zinc |
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| Authors: | Christian Blodau Markus Bauer Simona Regenspurg Donald Macalady |
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| Institution: | aLimnological Research Station and Department of Hydrology, University of Bayreuth, D-95440 Bayreuth, Germany;bDepartment of Chemistry & Geochemistry, Colorado School of Mines Golden, Colorado 80401, USA |
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| Abstract: | Information about the chemical electron accepting capacity (EAC) of dissolved organic matter (DOM) is scarce owing to a lack of applicable methods. We quantified the electron transfer from metallic Zn to natural DOM in batch experiments at DOC concentrations of 10–100 mg-C L− 1 and related it to spectroscopic information obtained from UV-, synchronous fluorescence, and FTIR- spectroscopy. The electron donating capacity of DOM and pre-reduced DOM was investigated using Fe(CN)63− as electron acceptor. Presence of DOM resulted in release of dissolved Zn, consumption of protons, and slower release of hydrogen compared to reaction of metallic Zn with water at pH 6.5. Comparison with reaction stoichiometry confirmed that DOM accepted electrons from metallic Zn. The release of dissolved Zn was dependent on pH, DOC concentration, ionic strength, and organic matter properties. The reaction appeared to be completed within about 24 h and was characterized by pseudo first order kinetics with rate constants of 0.5 to 0.8 h− 1. EAC per mass unit of carbon ranged from 0.22 mmol g− 1 C to 12.6 mmol g− 1 C. Depending on the DOM, a calculated 28–127% of the electrons transferred from metallic Zn to DOM could be subsequently donated to Fe(CN)63−. EAC decreased with DOC concentration, and increased with aromaticity, carboxyl, and phenolic content of the DOM. The results indicate that an operationally defined EAC of natural DOM can be quantified by reaction with metallic Zn and that DOM properties control the electron transfer. Shortcomings of the method are the coagulation and precipitation of DOM during the experiment and the production of hydrogen and dissolved Zn by reaction of metallic Zn with water, which may influence the determined EAC. |
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| Keywords: | DOM NOM Redox Humic acid FTIR Fluorescence Prussian Blue |
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