Effects of Sorption on Redox Properties of Natural Organic Matter.

Natural organic matter (NOM) is an important redox-active component of natural porous media and predominantly occurs in the sorbed state. Nevertheless, the effects of NOM sorption at minerals on its redox properties are unknown and thus are the major objective of this study. We report how adsorption of three different humic acids (HAs) to redox-inert sorbents (polar AlO and nonpolar DAX-8 resin) affects their electron-exchange capacities (EEC) and redox states. The electron-donating capacity of HAs sorbed at AlO increased by up to 200%, whereas the EEC of the remaining dissolved HA fractions decreased compared with their initial properties. Sorption at DAX-8, however, did not affect significantly the EEC of HAs. We rationalize these results by (i) preferential sorption of NOM components rich in redox-active groups (e.g., quinone, polyphenols) and (ii) surface-catalyzed polymerization of polyphenolic compounds. Our results demonstrate that even in the absence of electron exchange with the sorbent, adsorption to polar mineral surfaces considerably affects the redox properties of NOM. Quantification of the redox state and EEC of adsorbed NOM is thus crucial for assessing electron-transfer processes as well as organic carbon stabilization and sequestration in soils and sediments.