Macromolecular Characterization of Compound Selectivity for Oxidation and Oxidative Alterations of Dissolved Organic Matter by Manganese Oxide

Manganese (Mn) oxides can oxidize dissolved organic matter (DOM) and alter its chemical properties and microbial degradability, but the compound selectivity for oxidation and oxidative alterations remain to be determined. We applied ultrahigh mass spectrometry to catalog the macromolecular composition of Suwannee River fulvic acid (SRFA) before and after oxidation by a Mn oxide (δ-MnO2) at pH 4 or 6. Polycyclic aromatic hydrocarbons, polyphenols, and carbohydrates were more reactive in reducing δ-MnO2 than highly unsaturated and phenolic (HuPh) compounds and aliphatics, but highly abundant HuPh contributed the most (∼50%) to the overall reduction of δ-MnO2. On average, oxidized species had higher molecular weights, aromaticity, carbon unsaturation degree, nominal oxidation state of carbon, and oxygen and nitrogen contents but were lower in hydrogen content compared to unoxidized species. The oxidation decreased these molecular indices and oxygen and nitrogen contents but increased the hydrogen content, with stronger changes at the lower pH. This DOM oxidation on polar mineral surfaces was more selective but shared similar selectivity rules to adsorption. The abiotic oxidation resembles microbial oxidative degradation of organic matter, and Mn oxide–oxidizable carbon may be a useful index for detection and identification of labile organic carbon.