Asynchronous Reductive Release of Iron and Organic Carbon from Hematite-Humic Acid Complexes

Abstract:

Association with solid-phase iron plays an important role in the accumulation and stabilization of soil organic matter (SOM). Ferric minerals are subject to redox reactions, which can compromise the stability of iron-bound SOM. To date, there is limited information available concerning the fate of iron-bound SOM during redox reactions. In this study, we investigated the release kinetics of hematite-bound organic carbon (OC) during the abiotic reduction of hematite-humic acid (HA) complexes by dithionite, as an analog for the fate of iron-bound SOM in natural redox reactions. Carbon 1s near edge X-ray absorption fine structure (NEXAFS) spectroscopy was used to examine the ratio of the aromatic, phenolic and carboxylic/imide functional groups of the adsorbed OC before and after reduction. Our results indicate that the reductive release of iron obeyed first-order kinetics with release rate constants of 6.67×10^-3 to 13.0×10^-3 min^-1. The iron-bound OC was released rapidly during the initial stage with release rate constants of 0.011 to 1.49 min^-1, and then became stable with residual fractions of 4.6% to 58.2% between 120 and 240 min. The release rate of aromatic OC was much faster than for the non-aromatic fraction of HA, and 90% of aromatic OC was released within the first hour for most samples. The more rapid release of aromatic OC was attributed to its potential distribution on the outer layer because of steric effects and the possible reduction of quinoids. Our findings show that in the reductive reaction the mobilization of iron-bound organic carbon was asynchronous with the reduction of iron, and aromatic carbon was released more readily than other organic components. This study illustrates the importance of evaluating the stability of iron-bound SOM, especially under aerobic-anaerobic transition conditions.